Triazole derivatives

ABSTRACT

The present invention relates to novel triazole derivatives, to processes for preparing these compounds, to compositions comprising these compounds, and to the use thereof as biologically active compounds, especially for control of harmful microorganisms in crop protection and in the protection of materials and as plant growth regulators.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a §371 National Stage Application ofPCT/EP2014/057174, filed 9 Apr. 2014, which claims priority to EP13163595.5, filed 12 Apr. 2013.

BACKGROUND

Field of the Invention

The present invention relates to novel triazole derivatives, toprocesses for preparing these compounds, to compositions comprisingthese compounds, and to the use thereof as biologically activecompounds, especially for control of harmful microorganisms in cropprotection and in the protection of materials and as plant growthregulators.

Description of Related Art

It is already known that particular alkyl-substituted triazolederivatives can be used in crop protection as fungicides (cf. CN 1760193A). It is also known that particular triazole derivatives can be used inseveral pharmaceutical indications and in crop protection as fungicides(cf. WO-A 2012/177635, WO-A 2012/177638, WO-A 2012/177603, WO-A2012/177608, WO-A 2012/177725, WO-A 2012/177728).

Since the ecological and economic demands made on modern activeingredients, for example fungicides, are increasing constantly, forexample with respect to activity spectrum, toxicity, selectivity,application rate, formation of residues and favourable manufacture, andthere can also be problems, for example, with resistances, there is aconstant need to develop novel fungicidal compositions which haveadvantages over the known compositions at least in some areas.

SUMMARY

Accordingly, the present invention provides novel triazole derivativesof the formula (I)

wherein

-   R¹ represents substituted or non-substituted C₁-C₈-alkyl;    substituted or non-substituted C₄-C₈-cycloalkylalkyl; substituted or    non-substituted C₂-C₈-alkenyl; substituted or non-substituted    C₂-C₈-alkynyl;    and-   R² represents H, C₁-C₈-alkyl, —Si(R^(3a))(R^(3b))(R^(3c)),    —P(O)(OH)₂, —CH₂—O—P(O)(OH)₂, substituted or non-substituted    —C(O)—C₁-C₈-alkyl; substituted or non-substituted    —C(O)—C₃-C₇-cycloalkyl, substituted or non-substituted    —C(O)NH—C₁-C₈-alkyl; substituted or non-substituted    —C(O)N-di-C₁-C₈-alkyl; substituted or non-substituted    —C(O)O—C₁-C₈-alkyl;    and-   R^(3a), R^(3b), R^(3c) independent from each other represent a    substituted or non-substituted C₁-C₈-alkyl;    and-   X represents a substituted or non-substituted unsaturated 6-membered    heterocycle containing 1 or 2 nitrogen atom(s) as heteroatom(s) or a    benzannulated derivative thereof;    and its salts or N-oxides.

DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT

The salts or N-oxides of the triazole derivatives of formula (I) alsohave fungicidal properties.

Unless otherwise indicated the term “substituted or non-substituted” inthe definitions for R¹, R², R^(3a), R^(3b), R^(3c) and X given in theformulae of the present application and preferred ranges or embodimentsthereof preferably includes non-substituted or substituted by halogen;hydroxyl; cyano; amino; sulfanyl; pentafluoro-λ⁶-sulfanyl; C₁-C₈-alkyl;C₁-C₈-haloalkyl; C₁-C₈-alkyloxy; C₁-C₈-halogenalkyloxy; C₁-C₈-alkylthio;C₁-C₈-halogenalkylthio; tri(C₁-C₈-alkyl)silyl;tri(C₁-C₈-alkyl)silyl-C₁-C₈-alkyl; C₃-C₇-cycloalkyl;C₃-C₇-halogencycloalkyl; C₃-C₇-cycloalkenyl; C₃-C₇-halogencycloalkenyl;C₄-C₁₀-cycloalkylalkyl; C₄-C₁₀-halocycloalkylalkyl;C₆-C₁₂-cycloalkylcycloalkyl; C₁-C₈-alkyl-C₃-C₇-cycloalkyl;C₁-C₈-alkoxy-C₃-C₇-cycloalkyl; tri(C₁-C₈-alkyl)silyl-C₃-C₇-cycloalkyl;C₂-C₈-alkenyl; C₂-C₈-alkynyl; C₂-C₈-alkenyloxy; C₂-C₈-halogenalkenyloxy;C₃-C₈-alkynyloxy; C₃-C₈-halogenoalkynyloxy; C₁-C₈-alkylamino;C₁-C₈-halogenalkylamino; C₁-C₈-alkoxy; C₁-C₈-halogenoalkoxy;C₁-C₈-cyanoalkoxy; C₄-C₈-cycloalkylalkoxy; C₃-C₆-cycloalkoxy;C₁-C₈-alkylsulfanyl; C₁-C₈-halogenoalkylsulfanyl; C₁-C₈-alkykarbonyl;C₁-C₈-halogenoalkylcarbonyl; C₃-C₈-cycloalkylcarbonyl;C₃-C₈-halogenocycloalkylcarbonyl; C₁-C₈-alkylcarbamoyl;di-C₁-C₈-alkylcarbamoyl; N—C₁-C₈-alkyloxycarbamoyl;C₁-C₈-alkoxycarbamoyl; N—C₁-C₈-alkyl-C₁-C₈-alkoxycarbamoyl;C₁-C₈-alkoxycarbonyl; C₁-C₈-halogenoalkoxycarbonyl;C₃-C₈-cycloalkoxycarbonyl; C₂-C₈-alkoxyalkylcarbonyl;C₂-C₈-halogenoalkoxyalkylcarbonyl; C₃-C₁₀-cycloalkoxyalkylcarbonyl;C₁-C₈-alkylaminocarbonyl; di-C₁-C₈-alkylaminocarbonyl;C₃-C₈-cycloalkylaminocarbonyl; C₁-C₈-alkylcarbonyloxy;C₁-C₈-halogenoalkylcarbonyloxy; C₃-C₈-cycloalkylcarbonyloxy;C₁-C₈-alkylcarbonylamino; C₁-C₈-halogenoalkylcarbonylamino;C₁-C₈-alkylaminocarbonyloxy; di-C₁-C₈-alkylaminocarbonyloxy;C₁-C₈-alkyloxycarbonyloxy; C₁-C₈-alkylsulfinyl;C₁-C₈-halogenoalkylsulfinyl; C₁-C₈-alkylsulfonyl;C₁-C₈-halogenoalkylsulfonyl; C₁-C₈-alkylsulfonyloxy;C₁-C₈-halogenoalkylsulfonyloxy; C₁-C₈-alkylaminosulfamoyl;di-C₁-C₈-alkylaminosulfamoyl; (C₁-C₈-alkoxyimino)-C₁-C₈-alkyl;(C₃-C₇-cycloalkoxyimino)-C₁-C₈-alkyl; hydroxyimino-C₁-C₈-alkyl;(C₁-C₈-alkoxyimino)-C₃-C₇-cycloalkyl; hydroxyimino-C₃-C₇-cycloalkyl;(C₁-C₈-alkylimino)-oxy; (C₁-C₈-alkylimino)-oxy-C₁-C₈-alkyl;(C₃-C₇-cycloalkylimino)-oxy-C₁-C₈-alkyl;(C₁-C₆-alkylimino)-oxy-C₃-C₇-cycloalkyl;(C₁-C₈-alkenyloxyimino)-C₁-C₈-alkyl;(C₁-C₈-alkynyloxyimino)-C₁-C₈-alkyl; 2-oxopyrrolidin-1-yl,(benzyloxyimino)-C₁-C₈-alkyl; C₁-C₈-alkoxyalkyl; C₁-C₈-alkylthioalkyl;C₁-C₈-alkoxyalkoxyalkyl; C₁-C₈-halogenoalkoxyalkyl; benzyl; phenyl;5-membered heteroaryl; 6-membered heteroaryl; benzyloxy; phenyloxy;benzylsulfanyl; benzylamino; phenoxy; phenylsulfanyl; or phenylamino;wherein the benzyl, phenyl, 5-membered heteroaryl, 6-memberedheteroaryl, benzyloxy or phenyloxy may be optionally substituted by oneor more group(s) selected from the aforementioned list.

Preferably the term “substituted or non-substituted” in the definitionsfor R¹, R², R^(3a), R^(3b), R^(3c) and X preferably includesnon-substituted or substituted by halogen; cyano; C₁-C₈-alkyl;C₁-C₈-haloalkyl; C₁-C₈-alkoxy; C₁-C₈-halogenalkoxy;(C₁-C₈-alkoxyimino)-C₁-C₈-alkyl; C₃-C₇-cycloalkyl;C₃-C₇-halogencycloalkyl; C₂-C₈-alkenyl; or C₂-C₈-alkynyl.

The formula (I) provides a general definition of the triazolederivatives according to the invention. Preferred radical definitionsfor the formulae shown above and below are given below. Thesedefinitions apply to the end products of the formula (I) and likewise toall intermediates.

-   R¹ preferably represents substituted or non-substituted C₁-C₈-alkyl.-   R¹ more preferably represents non-substituted or    C₃-C₇-cycloalkyl-substituted C₁-C₈-alkyl.-   R¹ most preferably represents non-substituted or    C₃-C₇-cycloalkyl-substituted C₁-C₄-alkyl.

In preferred embodiments of the present invention R¹ represents anon-substituted C₁-C₈-alkyl, preferably a non-substituted C₁-C₄-alkyl,more preferably tert-butyl.

In another preferred embodiment of the present invention R¹ represents asubstituted C₃-C₇-cycloalkyl-substituted C₁-C₈-alkyl, preferably aC₃-C₇-cycloalkyl-substituted C₁-C₄-alkyl, more preferablycyclopropylmethyl, cyclopropyl-ethan-1-yl, cyclopropyl-ethan-2-yl.

In another preferred embodiment of the present invention R¹ represents asubstituted C₃-C₇-cycloalkylalkyl, preferably a substitutedcyclopropylalkyl wherein two substituents at the same or differentcarbon atom(s) can form together with the C₃-C₇-cycloalkyl, preferablythe cyclopropyl to which they are attached a substituted ornon-substituted bicycloalkyl.

In another preferred embodiment

-   R¹ preferably represents non-substituted or C₁-C₄-alkoxy-substituted    or C₃-C₇-cycloalkyl-substituted C₁-C₈-alkyl.-   R¹ more preferably represents non-substituted or    C₁-C₄-alkoxy-substituted or C₃-C₇-cycloalkyl-substituted    C₁-C₄-alkyl.-   X preferably represents a substituted or non-substituted unsaturated    6 membered heterocycle containing 1 or 2 nitrogen atom(s) as    heteroatom(s) or a benzannulated derivative thereof, with the    provisio that X does not represent 2-pyridinyl.-   X more preferably represents a substituted or non-substituted    3-pyridinyl, 4-pyridinyl, 4-pyrimidinyl, 5-pyrimidinyl,    pyrazin-2-yl, pyridazin-3-yl or pyridazin-4-yl, quinoline-2-yl,    quinoline-3-yl.-   X also more preferably represents a substituted or non-substituted    3-pyridinyl, 4-pyridinyl, 4-pyrimidinyl, 5-pyrimidinyl,    pyrazin-2-yl, pyridazin-3-yl, pyridazin-4-yl, quinoline-2-yl,    quinoline-3-yl or quinoline-4-yl.-   X most preferably represents substituted or non-substituted    3-pyridinyl, 4-pyridinyl, 4-pyrimidinyl, or 5-pyrimidinyl,    quinoline-2-yl, quinoline-3-yl.

In preferred embodiments of the present invention X representssubstituted or non-substituted 3-pyridinyl or 4-pyridinyl.

In another preferred embodiments of the present invention X representssubstituted 3-pyridinyl or 4-pyridinyl.

In another preferred embodiments of the present invention X represents3-pyridinyl or 4-pyridinyl substituted by at least one halogensubstituent.

In another preferred embodiments of the present invention X representssubstituted or non-substituted 2-pyridinyl.

In another preferred embodiments of the present invention X represents2-pyridinyl substituted by at least one halogen substituent.

For all definitions for X preference is given to such heterocycles whichdo not contain other heteroatom(s) than nitrogen atom(s).

-   R² preferably represents H, C₁-C₈-alkyl, substituted or    non-substituted —C(O)—C₁-C₈-alkyl.-   R² also preferably represents H, C₁-C₈-alkyl, substituted or    non-substituted —C(O)—C₁-C₈-alkyl or substituted or non-substituted    —C(O)O—C₁-C₈-alkyl.-   R² more preferably represents H.

In such embodiments of the present invention wherein R² represents—Si(R^(3a))(R^(3b))(R^(3c))—Si(R₃)₃

-   R^(3a), R^(3b), R^(3c) preferably represent independent from each    other methyl, ethyl or tert-butyl,-   R^(3a), R^(3b), R^(3c) more preferably represents methyl.

In another preferred embodiments of the present invention

-   R¹ represents non-substituted or C₁-C₄-alkoxy-substituted or    C₃-C₇-cycloalkyl-substituted C₁-C₈-alkyl, and-   R² represents H, C₁-C₈-alkyl, substituted or non-substituted    —C(O)—C₁-C₈-alkyl or substituted or non-substituted    —C(O)O—C₁-C₈-alkyl, and-   X represents a substituted or non-substituted 2-pyridinyl,    3-pyridinyl, 4-pyridinyl, 4-pyrimidinyl, 5-pyrimidinyl,    pyrazin-2-yl, pyridazin-3-yl, pyridazin-4-yl, quinoline-2-yl,    quinoline-3-yl or quinoline-4-yl.

In another preferred embodiments of the present invention

-   R¹ represents non-substituted or C₁-C₄-alkoxy-substituted or    C₃-C₇-cycloalkyl-substituted C₁-C₈-alkyl, and-   R² represents H or substituted or non-substituted    —C(O)O—C₁-C₈-alkyl, and-   X represents a substituted or non-substituted 2-pyridinyl,    3-pyridinyl, 4-pyridinyl, 4-pyrimidinyl, 5-pyrimidinyl,    pyrazin-2-yl, pyridazin-3-yl, pyridazin-4-yl, quinoline-2-yl,    quinoline-3-yl or quinoline-4-yl.

The radical definitions and explanations given above in general terms orstated within preferred ranges can, however, also be combined with oneanother as desired, i.e. including between the particular ranges andpreferred ranges. They apply both to the end products andcorrespondingly to precursors and intermediates. In addition, individualdefinitions may not apply.

Preference is given to those compounds of the formula (I) in which eachof the radicals have the abovementioned preferred definitions.

Particular preference is given to those compounds of the formula (I) inwhich each of the radicals have the abovementioned more preferreddefinitions.

Very particular preference is given to those compounds of the formula(I) in which each of the radicals have the above mentioned mostpreferred definitions.

In the definitions of the symbols given in the above formulae,collective terms were used which are generally representative of thefollowing substituents:

The definition C₁-C₈-alkyl comprises the largest range defined here foran alkyl radical. Specifically, this definition comprises the meaningsmethyl, ethyl, n-, isopropyl, n-, iso-, sec-, tert-butyl, and also ineach case all isomeric pentyls, hexyls, heptyls and octyls, such asmethyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl,2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl,2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl,2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl,2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl,1,3-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl,2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl,1,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl,1-ethyl-3-methylpropyl, n-heptyl, 1-methylhexyl, 1-ethylpentyl,2-ethylpentyl, 1-propylbutyl, octyl, 1-methylheptyl, 2-methylheptyl,1-ethylhexyl, 2-ethylhexyl, 1-propylpentyl and 2-propylpentyl, inparticular propyl, 1-methylethyl, butyl, 1-methylbutyl, 2-methylbutyl,3-methylbutyl, 1,1-dimethylethyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,pentyl, 1-methylbutyl, 1-ethylpropyl, hexyl, 3-methylpentyl, heptyl,1-methylhexyl, 1-ethyl-3-methylbutyl, 1-methylheptyl, 1,2-dimethylhexyl,1,3-dimethyloctyl, 4-methyloctyl, 1,2,2,3-tetramethylbutyl,1,3,3-trimethylbutyl, 1,2,3-trimethylbutyl, 1,3-dimethylpentyl,1,3-dimethylhexyl, 5-methyl-3-hexyl, 2-methyl-4-heptyl and1-methyl-2-cyclopropylethyl. A preferred range is C₁-C₄-alkyl, such asmethyl, ethyl, n-, isopropyl, n-, iso-, sec-, tert-butyl.

Halogen-substituted alkyl—referred to as C₁-C₈-haloalkyl—represents, forexample, C₁-C₈-alkyl as defined above substituted by one or more halogensubstituents which can be the same or different. PreferablyC₁-C₈-haloalkyl represents chloromethyl, dichloromethyl,trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl,chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl,1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl,2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl,2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl,1-fluoro-1-methylethyl, 2-fluoro-1,1-dimethylethyl,2-fluoro-1-fluoromethyl-1-methylethyl,2-fluoro-1,1-di(fluoromethyl)-ethyl, 3-chloro-1-methylbutyl,2-chloro-1-methylbutyl, 1-chlorobutyl, 3,3-dichloro-1-methylbutyl,3-chloro-1-methylbutyl, 1-methyl-3-trifluoromethylbutyl,3-methyl-1-trifluoromethylbutyl.

The definition C₂-C₈-alkenyl comprises the largest range defined herefor an alkenyl radical. Specifically, this definition comprises themeanings ethenyl, n-, isopropenyl, n-, iso-, sec-, tert-butenyl, andalso in each case all isomeric pentenyls, hexenyls, heptenyls, octenyls,1-methyl-1-propenyl, 1-ethyl-1-butenyl, 2,4-dimethyl-1-pentenyl,2,4-dimethyl-2-pentenyl. Halogen-substituted alkenyl—referred to asC₂-C₈-haloalkenyl—represents, for example, C₂-C₈-alkenyl as definedabove substituted by one or more halogen substituents which can be thesame or different.

The definition C₂-C₈-alkynyl comprises the largest range defined herefor an alkynyl radical. Specifically, this definition comprises themeanings ethynyl, n-, isopropynyl, n-, iso-, sec-, tert-butynyl, andalso in each case all isomeric pentynyls, hexynyls, heptynyls, octynyls.Halogen-substituted alkynyl—referred to as C₂-C₈-haloalkynyl—represents,for example, C₂-C₈-alkyl as defined above substituted by one or morehalogen substituents which can be the same or different.

The definition C₃-C₇-cycloalkyl comprises monocyclic saturatedhydrocarbyl groups having 3 to 7 carbon ring members, such ascyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.

The definition halogen-substituted cycloalkyl and halocycloalkylcomprises monocyclic saturated hydrocarbyl groups having 3 to 7 carbonring members, such as 1-fluoro-cyclopropyl and 1-chloro-cyclopropyl.

The definition bicycloalkyl comprises spirocyclic alkyl wherein twosubstituents at the same carbon atom of a C₃-C₇-cycloalkyl can formtogether with the carbon atom to which they are attached aC₃-C₇-cycloalkyl, this definition comprises for example the meaningspiro[2.2]pentyl The definition bicycloalkyl also comprises bicyclicalkyls wherein two substituents at different adjacent or non-adjacentcarbon atoms of a C₃-C₇-cycloalkyl can form together with the carbonatoms to which they are attached a C₃-C₇-cycloalkyl, this definitioncomprises for example the meaning bicyclo[2.2.1]heptane-2-yl,bicyclo[2.2.1]heptane-7-yl, bicyclo[4.1.0]heptane-2-yl,bicyclo[4.1.0]heptane-3-yl, bicyclo[4.1.0]heptane-7-yl The definitionbicycloalkyl also comprises bicyclic alkyls wherein two substituents atdifferent adjacent or non-adjacent carbon atoms of a C₃-C₇-cycloalkylcan form an alkylene bridge between the carbon atoms to which they areattached, this definition comprises for example the meaningbicyclo[2.2.1]hept-2-ene-2-yl, bicyclo[2.2.1]hept-2-ene-5-yl,bicyclo[2.2.1]hept-2-ene-7-yl.

The definition aryl comprises unsubstituted or substituted, aromatic,mono-, bi- or tricyclic ring, for example phenyl, naphthyl, anthracenyl(anthryl), phenanthracenyl (phenanthryl).

The definition 6-membered unsaturated heterocycle containing 1 or 2nitrogen atom(s) as heteroatom(s) comprises for example 2-pyridinyl,3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl,4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl.

The definition benzannulated derivative of 6-membered unsaturatedheterocycle containing 1 or 2 nitrogen atom(s) as heteroatom(s)comprises for example 2-quinolinyl, 3-quinolinyl, 4-quinolinyl,1-isoquinolinyl, 3-isoquinolinyl, 4-isoquinolinyl, 2-quinazolinyl,4-quinazolinyl, cinnolin-3-yl; cinnolin-4-yl; phthalazin-1-yl;phthalazin-4-yl; quinoxalin-2-yl; quinoxalin-3-yl.

The definition hetaryl or heteroaryl comprises unsubstituted orsubstituted, unsaturated heterocyclic 5- to 7-membered ring containingup to 4 heteroatoms selected from N, O and S: for example 2-furyl,3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 1-pyrrolyl,3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 1-pyrazolyl, 1H-imidazol-2-yl,1H-imidazol-4-yl, 1H-imidazol-5-yl, 1H-imidazol-1-yl, 2-oxazolyl,4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl,3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl,4-isothiazolyl, 5-isothiazolyl, 1H-1,2,3-triazol-1-yl,1H-1,2,3-triazol-4-yl, 1H-1,2,3-triazol-5-yl, 2H-1,2,3-triazol-2-yl,2H-1,2,3-triazol-4-yl, 1H-1,2,4-triazol-3-yl, 1H-1,2,4-triazol-5-yl,1H-1,2,4-triazol-1-yl, 4H-1,2,4-triazol-3-yl, 4H-1,2,4-triazol-4-yl,1H-tetrazol-1-yl, 1H-tetrazol-5-yl, 2H-tetrazol-2-yl, 2H-tetrazol-5-yl,1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl,1,2,4-thiadiazol-5-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl,1,2,3-oxadiazol-4-yl, 1,2,3-oxadiazol-5-yl, 1,2,3-thiadiazol-4-yl,1,2,3-thiadiazol-5-yl, 1,2,5-oxadiazol-3-yl, 1,2,5-thiadiazol-3-yl,2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl,2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl,1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl, 1,2,4-triazin-5-yl,1,2,4-triazin-6-yl.

The definition heterocycloalkyl comprises saturated or partiallyunsaturated mono-, bi- or tricyclic ring system consisting of C-atomsand containing up to 4 heteroatoms selected from N, O and S: for exampleaziridinyl, pyrrolidinyl, dihydropyridyl, piperidinyl, piperazinyl,morpholinyl, thiomorpholinyl, tetrahydrofuranyl, tetrahydrothiofuranyl,tetrahydropyranyl, pyranyl, isoxazolidinyl, isoxazolinyl, pyrazolinyl,dihydropyrrolyl, tetrahydropyridinyl, dioxolanyl, dioxanyl,oxathiolanyl, oxathianyl, dithhiolanyl, dithianyl.

Optionally substituted radicals may be mono- or polysubstituted, wherein the case of polysubstitution, the substituents may be identical ordifferent.

Unless indicated otherwise, a group or a substituent which issubstituted according to the invention preferably can be substituted byone or more group(s) selected from the list consisting of halogen; SH;nitro; hydroxyl; cyano; amino; sulfanyl; pentafluoro-λ⁶-sulfanyl;formyl; formyloxy; formylamino; carbamoyl; N-hydroxycarbamoyl;carbamate; (hydroxyimino)-C₁-C₆-alkyl; C₁-C₈-alkyl; C₁-C₈-halogenalkyl;C₁-C₈-alkyloxy; C₁-C₈-halogenalkyloxy; C₁-C₈-alkylthio;C₁-C₈-halogenalkylthio; tri(C₁-C₈-alkyl)silyl;tri(C₁-C₈-alkyl)silyl-C₁-C₈-alkyl; C₃-C₇-cycloalkyl;C₃-C₇-halocycloalkyl; C₃-C₇-cycloalkenyl; C₃-C₇-halocycloalkenyl;C₄-C₁₀-cycloalkylalkyl; C₄-C₁₀-halocycloalkylalkyl;C₆-C₁₂-cycloalkylcycloalkyl; tri(C₁-C₈-alkyl)silyl-C₃-C₇-cycloalkyl;C₁-C₈-halogenoalkyl; C₃-C₇-halogenocycloalkyl; C₂-C₈-alkenyl;C₂-C₈-alkynyl; C₂-C₈-alkenyloxy; C₂-C₈-halogenalkenyloxy;C₂-C₈-alkynyloxy; C₁-C₈-alkylamino; di-C₁-C₈-alkylamino;C₁-C₈-halogenalkylamino; di-C₁-C₈-halogenalkylamino;C₁-C₈-alkylaminoalkyl; di-C₁-C₈-alkylaminoalkyl; C₁-C₈-alkoxy;C₁-C₈-halogenoalkoxy; C₁-C₈-cyanoalkoxy; C₄-C₈-cycloalkylalkoxy;C₃-C₆-cycloalkoxy; C₂-C₈-alkoxyalkoxy; C₁-C₈-alkylcarbonylalkoxy;C₁-C₈-alkylsulfanyl; C₁-C₈-halogenoalkylsulfanyl; C₂-C₈-alkenyloxy;C₂-C₈-halogenoalkenyloxy; C₃-C₈-alkynyloxy; C₃-C₈-halogenoalkynyloxy;C₁-C₈-alkylcarbonyl; C₁-C₈-halogenoalkylcarbonyl;C₃-C₈-cycloalkylcarbonyl; C₃-C₈-halogenocycloalkylcarbonyl;C₁-C₈-alkylcarbamoyl; di-C₁-C₈-alkylcarbamoyl;N—C₁-C₈-alkyloxycarbamoyl; C₁-C₈-alkoxycarbamoyl;N—C₁-C₈-alkyl-C₁-C₈-alkoxycarbamoyl; C₁-C₈-alkoxycarbonyl;C₁-C₈-halogenoalkoxycarbonyl; C₃-C₈-cycloalkoxycarbonyl;C₂-C₈-alkoxyalkylcarbonyl; C₂-C₈-halogenoalkoxyalkylcarbonyl;C₃-C₁₀-cycloalkoxyalkylcarbonyl; C₁-C₈-alkylaminocarbonyl;di-C₁-C₈-alkylaminocarbonyl; C₃-C₈-cycloalkylaminocarbonyl;C₁-C₈-alkylcarbonyloxy; C₁-C₈-halogenoalkylcarbonyloxy;C₃-C₈-cycloalkylcarbonyloxy; C₁-C₈-alkylcarbonylamino;C₁-C₈-halogenoalkylcarbonylamino; C₁-C₈-alkylaminocarbonyloxy;di-C₁-C₈-alkylaminocarbonyloxy; C₁-C₈-alkyloxycarbonyloxy;C₁-C₈-alkylsulfinyl; C₁-C₈-halogenoalkylsulfinyl; C₁-C₈-alkylsulfonyl;C₁-C₈-halogenoalkylsulfonyl; C₁-C₈-alkylsulfonyloxy;C₁-C₈-halogenoalkylsulfonyloxy; C₁-C₈-alkylaminosulfamoyl;di-C₁-C₈-alkylaminosulfamoyl; (C₁-C₈-alkoxyimino)-C₁-C₈-alkyl;(C₃-C₇-cycloalkoxyimino)-C₁-C₈-alkyl; hydroxyimino-C₁-C₈-alkyl;(C₁-C₈-alkoxyimino)-C₃-C₇-cycloalkyl; hydroxyimino-C₃-C₇-cycloalkyl;(C₁-C₈-alkylimino)-oxy; (C₁-C₈-alkylimino)-oxy-C₁-C₈-alkyl;(C₃-C₇-cycloalkylimino)-oxy-C₁-C₈-alkyl;(C₁-C₆-alkylimino)-oxy-C₃-C₇-cycloalkyl;(C₁-C₈-alkenyloxyimino)-C₁-C₈-alkyl;(C₁-C₈-alkynyloxyimino)-C₁-C₈-alkyl; 2-oxopyrrolidin-1-yl,(benzyloxyimino)-C₁-C₈-alkyl; C₁-C₈-alkoxyalkyl; C₁-C₈-alkylthioalkyl;C₁-C₈-alkoxyalkoxyalkyl; C₁-C₈-halogenoalkoxyalkyl; benzyl; phenyl;5-membered heteroaryl; 6-membered heteroaryl; benzyloxy; phenyloxy;benzylsulfanyl; benzylamino; phenoxy; phenylsulfanyl; or phenylamino;wherein the benzyl, phenyl, 5-membered heteroaryl, 6-memberedheteroaryl, benzyloxy or phenyloxy may be optionally substituted by oneor more group(s) selected from the aforementioned list.

The definition halogen comprises fluorine, chlorine, bromine and iodine.

In a preferred embodiment, according to the present inventionsubstituted C₁-C₈-alkyl, C₂-C₈-alkenyl, C₂-C₈-alkynyl orC₄-C₈-cycloalkylalkyl does not represent C₁-C₈-alkyl, C₂-C₈-alkenyl,C₂-C₈-alkynyl or C₄-C₈-cycloalkylalkyl substituted by one or morehalogen substituents, so that substituted C₁-C₈-alkyl, C₂-C₈-alkenyl,C₂-C₈-alkynyl or C₄-C₈-cycloalkylalkyl does not representC₁-C₈-haloalkyl, C₂-C₈-haloalkenyl, C₂-C₈-haloalkynyl,C₃-C₆-halocycloalkyl-C₁-C₄-alkyl, C₃-C₆-halocycloalkyl-C₁-C₄-haloalkylor C₃-C₆-cycloalkyl-C₁-C₄-haloalkyl

If appropriate, the compounds according to the invention can be presentas mixtures of different possible isomeric forms, in particular ofstereoisomers, such as, for example, E and Z, threo and erythro, andalso optical isomers, and, if appropriate, also of tautomers. What isclaimed are both the E and the Z isomers, and also the threo anderythro, and the optical isomers, any mixtures of these isomers, and thepossible tautomeric forms.

If appropriate, the compounds of the present invention can exist in oneor more optical or chiral isomer forms depending on the number ofasymmetric centres in the compound.

The invention thus relates equally to all the optical isomers and totheir racemic or scalemic mixtures (the term “scalemic” denotes amixture of enantiomers in different proportions) and to the mixtures ofall the possible stereoisomers, in all proportions. The diastereoisomersand/or the optical isomers can be separated according to the methodswhich are known per se by the man ordinary skilled in the art.

If appropriate, the compounds of the present invention can also exist inone or more geometric isomer forms depending on the number of doublebonds in the compound. The invention thus relates equally to allgeometric isomers and to all possible mixtures, in all proportions. Thegeometric isomers can be separated according to general methods, whichare known per se by the man ordinary skilled in the art.

If appropriate, the compounds of the present invention can also exist inone or more geometric isomer forms depending on the relative position(syn/anti or cis/trans) of the substituents of ring B. The inventionthus relates equally to all syn/anti (or cis/trans) isomers and to allpossible syn/anti (or cis/trans) mixtures, in all proportions. Thesyn/anti (or cis/trans) isomers can be separated according to generalmethods, which are known per se by the man ordinary skilled in the art.

The compounds of formula (I) wherein X is substituted by a hydroxy, asulfanyl or an amino substituent may be found in its tautomeric formresulting from the shift of the proton of said hydroxy, sulfanyl oramino group. All tautomeric forms of such compounds of the presentinvention) wherein X is substituted by a hydroxy, a sulfanyl or an aminosubstituent are also part of the present invention.

Illustration of the Processes and Intermediates

The present invention furthermore related to processes for preparingcompounds of formula (I). The present invention furthermore relates tointermediates such as compounds of formulae (V), (XII), (XV) and thepreparation thereof.

The compounds (I) can be obtained by various routes in analogy to priorart processes known (see e.g. EP-A 461 502, DE-A 40 27 608, DE-A 32 35935 and references therein) and by synthesis routes shown schematicallybelow and in the experimental part of this application. Unless indicatedotherwise, the radicals X, R¹, R² and R³ have the meanings given abovefor the compounds of formula (I). These definitions apply not only tothe end products of the formula (I) but likewise to all intermediates.

Process A (Scheme 1):

-   Y=—H or —OH-   Z=halogen, —OSO₂—C₁-C₈-alkyl, —OSO₂-aryl, —OP(O)(O—C₁-C₈-alkyl)₂ or    —OP(O)(O-aryl)₂, preferably —Cl or —Br A=halogen, preferably —Cl-   E=—O—C₁-C₈-alkyl, preferably —O-methyl, —O-ethyl; —O-aryl;    —S—C₁-C₈-alkyl; —S-aryl; —NHR^(a); —NR^(a)R^(b); R^(a): is aryl,    C₁-C₈-alkyl or C₃-C₇-cycloalkyl, R^(b): is C₁-C₈-alkyl or    C₁-C₈-alkyloxy, preferably —NMe₂, —NMeOMe; or heterocyclic leaving    groups, such as imidazole, triazole and hydroxybenzotriazole.

Compounds (IIa) and/or (III) are either commercially available orproducible by processes described in the literature (see, for example,“Comprehensive Heterocyclic Chemistry III”, Pergamon Press, 2008; vol.7, pages 101-169; 217-308 & vol. 7, pages 1-331 and references citedtherein; “Comprehensive Heterocyclic Chemistry II”, Pergamon Press,1996; vol. 5, pages 37-243 & vol. 6, pages 1-278 and references citedtherein; “Comprehensive Heterocyclic Chemistry I”, Pergamon Press, 1984;vol. 2, pages 395-510 & vol. 3, pages 1-197 and references citedtherein; “Comprehensive Heterocyclic Chemistry III”, Pergamon Press,2008; vol. 3, pages 45-388 & vol. 4, pages 1-364 and references citedtherein; “Comprehensive Heterocyclic Chemistry II”, Pergamon Press,1996; vol. 2, pages 39-257 & vol. 3, pages 1-220 and references citedtherein; “Comprehensive Heterocyclic Chemistry I”, Pergamon Press, 1984;vol. 4, pages 155-376 & vol. 5, pages 167-498 and references citedtherein).

The compounds (IIa) (Scheme 1) can be converted by means of methodsdescribed in the literature to the corresponding compounds (III) andsubsequently to compounds (V). In a first process, for example,compounds (IIa) are halogenated.

In case Y stands for hydrogen, the compounds (IIa) can be halogenatede.g. with Bromo- or Chlorosuccinimide (see e.g. WO-A 2011/012622, WO-A2008/003622, WO-A 2005/111003; Synthesis, 18, 2008, 2996 and referencescited therein), preferably in the presence of a radical initiator suchas Azobisisobutyronitrile or dibenzoyl peroxide and in the presence ofan organic solvent, e.g. a chlorinated organic solvent such astetrachloromethane. Alternatively, compounds (IIa) undergo side-chainhalogenation in the presence of bromine or chlorine (see e.g. EP 557967)to obtain compounds (III). Optionally, a radical initiator such asAzobisisobutyronitrile or dibenzoyl peroxide can be used.

Alternatively, compounds (IIa) are reacted with a base, e.g. methyllithium, and subsequently with a halogen source such as Magnesiumbromideto obtain compounds (III) (see e.g. WO-A 2012/087784)

Compounds (IIa) where Y stands for —OH are reacted with halogenatingagents, such as PBr₃, PCl₃ or thionyl chloride, to obtain compounds(III) (see e.g. WO-A 2009/153554, Bioorganic & Medicinal ChemistryLetters, 22, 2012, 901-906, WO-A 2010/132999 and references citedtherein). Alternatively, compounds (IIa) can be reacted with sulfonylhalides, such as e.g. Mesylchloride or Tosylchloride, or with phosphonicacid halides, such as e.g. diphenylphosphoryl chloride, to obtain therespective sulfonates and phosphates (see e.g. J. Org. Chem. 1992, 57,5425-5431 and references cited therein)

The compounds (III) can subsequently be reacted with compounds (IV) or(VI) wherein A and E represent a replaceable group such as halide, —OR,NHR^(a) or NR^(a)R^(b), preferably chloro, —O-methyl, —O— ethyl, —NMe₂or —NMeOMe. To obtain compounds (V), compounds (III) are reacted in afirst step with e g Zink, Magnesium or isopropylmagnesium chloride,followed by a carbonyl compound (IV) or (VI) preferably under anhydrousconditions and optionally in the presence of a metal catalyst, such aspalladium- or nickel-based catalysts. The metal catalyst can be usedsuch as (Ph₃P)₂PdCl₂ (e.g. WO-A 2012/087784, EP-A 461 502), PEPPSI-IPr(Chem. Eur. J. 2006, 12, 4743-4748) or prepared in-situ by the mixing ofa metals salt (e.g. Pd(OAc)₂) and a ligand (such as e.g. PPh₃,2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (S-Phos)). The Insertionof the metal can be enhanced by the addition of ionic salts, such asLiBr, LiCl, LiI, CuI, Zn(OPiv)₂, MgCl₂, CuCN (see e.g. DissertationAlbrecht Metzer 2010 (University Munich); Angew. Chem. Int. Ed. 2011,50, 9205-9209), or by activation of the metal using halogenated alkanes(1,2-dibromoethane) or halogenated alkylsilanes (TMSCl). Alternativelythis sequence may be carried out in a one-pot fashion (see e.g. Belleret al., Chem. Asian J., 2011, 7(1) 40-44).

The reaction can be performed at temperatures between room temperatureand refluxing temperature of the solvent.

As the solvent, all common solvents inert under the reaction conditions,such as for example ethers (such as e.g. tetrahydrofurane, diethylether) can be used and the reaction can be effected in mixtures of twoor more of these solvents.

Process B (Scheme 2):

-   A=halogen, preferably Cl-   E=—O—C₁-C₈-alkyl, preferably —O-methyl, —O-ethyl; —O-aryl;    —S—C₁-C₈-alkyl; —S-aryl; —NHR^(a); —NR^(a)R^(b); R^(a): is aryl,    C₁-C₈-alkyl or C₃-C₇-cycloalkyl, R^(b): is C₁-C₈-alkyl or    C₁-C₈-alkyloxy, preferably —NMe₂, —NMeOMe; or heterocyclic leaving    groups, such as imidazole, triazole and hydroxybenzotriazole.

Compounds (IIb) are either commercially available or producible byprocesses described in the literature (see, for example, “ComprehensiveHeterocyclic Chemistry III”, Pergamon Press, 2008; vol. 7, pages101-169; 217-308 & vol. 7, pages 1-331 and references cited therein;“Comprehensive Heterocyclic Chemistry II”, Pergamon Press, 1996; vol. 5,pages 37-243 & vol. 6, pages 1-278 and references cited therein;“Comprehensive Heterocyclic Chemistry I”, Pergamon Press, 1984; vol. 2,pages 395-510 & vol. 3, pages 1-197 and references cited therein;“Comprehensive Heterocyclic Chemistry III”, Pergamon Press, 2008; vol.3, pages 45-388 & vol. 4, pages 1-364 and references cited therein;“Comprehensive Heterocyclic Chemistry II”, Pergamon Press, 1996; vol. 2,pages 39-257 & vol. 3, pages 1-220 and references cited therein;“Comprehensive Heterocyclic Chemistry I”, Pergamon Press, 1984; vol. 4,pages 155-376 & vol. 5, pages 167-498 and references cited therein).

There are numerous literature methods for the preparation of ketones(see e.g. WO-A 2012/055942, WO-A 2012/100342, WO-A 2012/087784, WO-A2012/087833, US-A 2012/0010190, Dalton Transaction, 2011, 2366-2374,Journal of the American Chemical Society, 1955, 3858-3860, Journal ofthe American Chemical Society, 1937, 1494-1497, WO-A 2012/085815, WO-A2011/042389, WO-A 2003/026663, Heterocycles, 1998, 2103-2109, Bioorganic& Medicinal Chemistry Letters, 2010, 2634-2640).

In general, it is possible to prepare compounds of the formula (V) fromcorresponding compounds (IIb) and (IV) and/or from correspondingcompounds (IIb) and (VI) with suitable groups A and E (see Scheme 2,process B). Compounds (IIb) are optionally reacted sequentially with abase, e.g. n-butyllithium, lithium-diisopropylamide, lithiumbis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, potassiumbis(trimethylsilyl)amide sodium amide, potassium amide, potassiumtert-butoxide, methyl lithium, TMP₂Zn.2MgCl₂.2LiCl (see e.g.Dissertation Albrecht Metzer 2010, University Munich), followed bycompounds (IV) or (VI), preferably under anhydrous conditions.Optionally, the reaction of compounds (IIb) and compounds (IV) or (VI)is carried out in the presence of a base in a one-pot fashion. Thepossible groups for A and E are, for example, halide, —OR, NHR^(a) orNR^(a)R^(b), preferably chloro, —O-methyl, —O-ethyl, —NMe₂ or —NMeOMe,etc., which can act as appropriate leaving groups to form the desiredketones (V) under suitable reaction conditions (Scheme 2).

In an alternative route compounds (IIb) are reacted with compounds (VII)in the presence of a base, e.g. phenyl lithium or methyl lithium, toobtain compounds (V) (see e.g. Journal of the American Chemical Society,2011, 11194-11204; Journal of Medicinal Chemistry 1963, 205-207 andreferences cited therein).

Process C (Scheme 3):

-   Z=halogen, preferably Cl or Br-   n=0,1-   M=Li, MgZ, ZnZ, Si(C₁-C₈-alkyl)₃, Sn(C₁-C₈-alkyl)₃-   Z^(M)=halogen, hydroxyl preferably Cl or Br

One means of preparing compounds of the formula (V) from correspondingcompounds (VIII) with the compounds (IX) or (X) or (XI) is shown inScheme 3 (Process C). Compounds (X) include compounds (Xa), (Xb) and(Xc)

Compounds (VIII) are either commercially available or producible byprocesses described in the literature (see, for example, “ComprehensiveHeterocyclic Chemistry III”, Pergamon Press, 2008; vol. 7, pages101-169; 217-308 & vol. 7, pages 1-331 and references cited therein;“Comprehensive Heterocyclic Chemistry II”, Pergamon Press, 1996; vol. 5,pages 37-243 & vol. 6, pages 1-278 and references cited therein;“Comprehensive Heterocyclic Chemistry I”, Pergamon Press, 1984; vol. 2,pages 395-510 & vol. 3, pages 1-197 and references cited therein;“Comprehensive Heterocyclic Chemistry III”, Pergamon Press, 2008; vol.3, pages 45-388 & vol. 4, pages 1-364 and references cited therein;“Comprehensive Heterocyclic Chemistry II”, Pergamon Press, 1996; vol. 2,pages 39-257 & vol. 3, pages 1-220 and references cited therein;“Comprehensive Heterocyclic Chemistry I”, Pergamon Press, 1984; vol. 4,pages 155-376 & vol. 5, pages 167-498 and references cited therein).

Compounds (IX), (X) and (XI) are either commercially available orproducible by processes described in the literature (see, for example,WO-A 2010/029066; Chemische Berichte, 1986, 2995-3026 and referencescited therein).

A compound having the general formula (V) can be synthesized analogouslyto methods described in the literature (see, for example Organicletters, 2009, 1773-1775; European Journal of Organic Chemistry, 2011,1570-1574), by a coupling reaction of a compound with the correspondinggeneral formula (VIII) with a substrate of the general formula (IX), (X)or (XI) where Z is halogen, preferably chlorine or bromine.

Compounds (VIII) are reacted with compounds of the general structure(IX) or (X) to obtain compounds (V) analogously to methods described inthe literature (e.g. Organic letters, 2009, 1773-1775, European Journalof Organic Chemistry, 2011, 1570-1574, Chemical & PharmaceuticalBulletin, 1970, 1457-1464, Chemical & Pharmaceutical Bulletin, 1980,337-342, WO-A 2005/044785). Those reactions can be optionally carriedout in the presence of a catalyst and a base.

As catalysts for the reaction various metal based catalysts can be usedwhich are either used directly or being in situ prepared from a metalprecursor (e.g. Pd₂dba₃, Pd(OAc)₂) and a ligand (e.g. phosphine basedligands like Xanthphos, 2-(dicyclohexylphosphino)-2′-methylbiphenyl,2-Diphenylphosphino-2′-(N,N-dimethylamino)biphenyl,tri-t-butylphosphine, Tri-o-tolylphosphine) (see e.g. WO-A 2008/147544,WO-A 2005/027837).

As bases various organic and inorganic bases can be used such aspotassium phosphate, base, e.g. sodium amide, sodium hydride or sodiumtert-butoxide. Alternatively, silicon containing bases can be used (e.g.NaHMDS, KHMDS, LiHMDS).

Compounds (VIII) are reacted with compounds of the general structure(XI) to obtain compounds (V) analogously to methods described in theliterature (e.g. WO-A 2012/080476). The intermediary alkines can befurther converted to the corresponding ketones (V) by methods known inthe literature (see e.g. Chemistry—A European Journal, 2011, 1261-1267;European Journal of Organic Chemistry, 2008, 5277-5282; Journal of theChemical Society, 1944, 612-615 and references cited therein).

Process D (Scheme 4):

The compounds (V) (Scheme 4) can be converted by means of methodsdescribed in the literature to the corresponding compounds (XII) (seee.g. EP-A 461 502, DE-A 33 15 681, EP-A 291 797). Intermediates (V) arepreferably reacted with trimethylsulfoxonium- ortrimethylsulfonium-salts, preferably trimethylsulfoxonium halides,trimethylsulfonium halides, trimethylsulfoxonium methylsulfates ortrimethylsulfonium methylsulfates, preferably in the presence of a basesuch as sodium hydroxide.

Process E (Scheme 5):

Alternatively, compounds (V) can be first converted to the correspondingolefins (XIII), followed by an epoxidation to obtain epoxides (XII) (seee.g. EP-A 291 797).

Process F (Scheme 6):

-   G=halogen or hydrogen-   A=halogen, O—SO₂—C₁-C₈-alkyl or O—SO₂-aryl, preferably Cl or Br

Alternatively, a compound having the general formula (XII) can besynthesized analogously to methods described in the literature by acoupling reaction of a compound having the corresponding general formula(IIc) with a substrate of the general formula (XIV) (see e.g. DE-A 40 27608, WO-A 93/02086, WO-A 93/12121, Journal of Organic Chemistry, 2001,2149-2153 and references cited therein).

Compounds (IIc) are either commercially available or producible byprocesses described in the literature (see, for example, “ComprehensiveHeterocyclic Chemistry III”, Pergamon Press, 2008; vol. 7, pages101-169; 217-308 & vol. 7, pages 1-331 and references cited therein;“Comprehensive Heterocyclic Chemistry II”, Pergamon Press, 1996; vol. 5,pages 37-243 & vol. 6, pages 1-278 and references cited therein;“Comprehensive Heterocyclic Chemistry I”, Pergamon Press, 1984; vol. 2,pages 395-510 & vol. 3, pages 1-197 and references cited therein;“Comprehensive Heterocyclic Chemistry III”, Pergamon Press, 2008; vol.3, pages 45-388 & vol. 4, pages 1-364 and references cited therein;“Comprehensive Heterocyclic Chemistry II”, Pergamon Press, 1996; vol. 2,pages 39-257 & vol. 3, pages 1-220 and references cited therein;“Comprehensive Heterocyclic Chemistry I”, Pergamon Press, 1984; vol. 4,pages 155-376 & vol. 5, pages 167-498 and references cited therein).

If G stands for halogen, preferably chloride or bromide, compounds (IIc)are first transformed into Grignard reagents by the reaction withmagnesium or with halogen/metal exchange reagents such asisopropylmagnesium halides and subsequently reacted with ketones (XIV)preferably under anhydrous conditions to obtain compounds of the generalformula (XV) (see e.g. DE4027608). Alternatively, if G stands forhalogen, the halides (IIc) can be converted to the corresponding zincreagents and subsequently reacted with ketones (XIV) (e.g. ChemComm,2008, 5824-5826; Journal of Organic Chemistry, 2004, 908-914 andreferences cited therein).

In an alternative route compounds (IIc) (G=hydrogen) are reacted withcompounds (XIV) preferably in the presence of a base. Compounds (IIc)(G=hydrogen) are optionally reacted with a base upfront, e.g.n-butyllithium, lithium-diisopropylamide, lithiumbis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, potassiumbis(trimethylsilyl)amide sodium amide, potassium amide, potassiumtert-butoxide, methyl lithium, TMP₂Zn.2MgCl₂.2LiCl (see e.g.Dissertation Albrecht Metzer 2010, University Munich), followed bycompounds of the general structure (XIV) preferably under anhydrousconditions. The possible groups for A are, for example, halides whichcan act as appropriate leaving groups to form the desired compounds(XII) under suitable reaction conditions.

Process G (Scheme 7):

-   A=halogen, O—SO₂—C₁-C₈-alkyl or O—SO₂-aryl, preferably Cl or Br

A compound having the general formula (XV) can be synthesizedanalogously to methods described in the literature by a couplingreaction of a compound having the corresponding general formula (IIc)with a substrate of the general formula (XIV) (see e.g. DE-A 40 27 608,WO-A 93/02086, WO-A 93/12121, Journal of Organic Chemistry, 2001,2149-2153).

If G stands for halogen, preferably chloride or bromide, compounds (IIc)are first transformed into Grignard reagents by the reaction withmagnesium or with halogen/metal exchange reagents, such asisopropylmagnesium halides, and subsequently reacted with ketones (XIV)preferably under anhydrous conditions to obtain compounds of the generalformula (XV) (see e.g. DE4027608). Alternatively, if G stands forhalogen, the halides (IIc) can be converted to the corresponding zincreagents and subsequently reacted with ketones (XIV) (e.g. ChemComm,2008, 5824-5826; Journal of Organic Chemistry, 2004, 908-914 andreferences cited therein).

In an alternative route compounds (IIc) (G=hydrogen) are reacted withcompounds (XIV) preferably in the presence of a base. Compounds (IIc)(G=hydrogen) are optionally reacted with a base upfront, e.g.n-butyllithium, lithium-di-isopropylamide, lithiumbis(trimethylsilyl)amide, methyl lithium, followed by compounds of thegeneral structure (XIV) preferably under anhydrous conditions. Thepossible groups for A are, for example, halides which can act asappropriate leaving groups to form the desired compounds (XV) undersuitable reaction conditions.

Process H (Scheme 8):

The compounds (XII) obtained according to Process D, E or F can beconverted by means of methods described in the literature to thecorresponding compounds (Ia) (see e.g. DE-A 40 27 608, EP-A 461 502,DE-A 33 15 681, EP-A 291 797, WO9529901, EP0291797). The startingmaterials (XII) can be reacted with 1H-1,2,4-triazole (XVI) preferablyin the presence of a base, such as potassium carbonate and/or potassiumtert-butoxide, and preferably in the presence of an organic solvent,such as DMF, to obtain compounds (Ia).

Process I (Scheme 9):

-   A=halogen, O—SO₂—C₁-C₈-alkyl or O—SO₂-aryl, preferably Cl or Br

The compounds (XV) obtained according to Process G can be converted bymeans of methods described in the literature to the correspondingcompounds (Ia) (see e.g. DE-A 40 27 608). The starting materials (XV)can be reacted with 1H-1,2,4-triazole (XVI) preferably in the presenceof a base, such as potassium carbonate and/or potassium tert-butoxide,and preferably in the presence of an organic solvent, such as DMF, toobtain compounds (Ia).

Process J (Scheme 10):

-   G=halogen or hydrogen

Many triazole ketones of the formula (XVII) are known or can be preparedby literature known methods (e.g. DE-A 24 31 407, DE-A 26 10 022, DE-A26 38 470, DE-A 42 04 816, EP-A 0 470 463, U.S. Pat. No. 4,486,218, DE-A31 44 670). The compounds of the formula (XVII) which have not hithertobeen described in the literature can be prepared by customary methods.For instance, they are obtained by reacting the correspondinghalo-ketones with 1H-1,2,4-triazole in the presence of an acid-bindingagent.

In a process according to Scheme 10, for example, ketones (XVII) arereacted with derivatives (IIc), wherein G stands for halogen orhydrogen. If G stands for halogen, compounds (IIc) are first transformedinto Grignard reagents by the reaction with magnesium or withtransmetallation reagents such as isopropylmagenesium halides andsubsequently reacted with ketone (XVII), preferably under anhydrousconditions to obtain compounds (Ia).

In case G stands for hydrogen, compounds (IIc) can be reacted with anorganolithium reagent such as methyllithium or n-butyllithium preferablyunder anhydrous conditions to obtain a lithiated species. Optionally, abase such as lithiumdiisopropylamide or lithiumbis(trimethylsilyl)amide, can be used. The obtained intermediates aresubsequently reacted with ketones (XVII), preferably under anhydrousconditions to obtain compounds of the general formula (Ia).

Process K (Scheme 11):

-   G=halogen or hydrogen

The compounds (XVII) (Scheme 11) can be converted by means of methodsdescribed in the literature to the corresponding compounds (XVIII) (seee.g. DE-A 31 11 238, DE-A 33 07 217). Compounds of the general formula(XVII) are preferably reacted with trimethylsulfoxonium halides,trimethylsulfonium halides, trimethylsulfoxonium methylsulfates ortrimethylsulfonium methylsulfates, preferably in the presence of a base,such as sodium hydroxide, to obtain compounds (XVIII).

Compounds (XIX) are either commercially available or producible byprocesses described in the literature (see, for example, “ComprehensiveHeterocyclic Chemistry III”, Pergamon Press, 2008; vol. 7, pages101-169; 217-308 & vol. 7, pages 1-331 and references cited therein;“Comprehensive Heterocyclic Chemistry II”, Pergamon Press, 1996; vol. 5,pages 37-243 & vol. 6, pages 1-278 and references cited therein;“Comprehensive Heterocyclic Chemistry I”, Pergamon Press, 1984; vol. 2,pages 395-510 & vol. 3, pages 1-197 and references cited therein;“Comprehensive Heterocyclic Chemistry III”, Pergamon Press, 2008; vol.3, pages 45-388 & vol. 4, pages 1-364 and references cited therein;“Comprehensive Heterocyclic Chemistry II”, Pergamon Press, 1996; vol. 2,pages 39-257 & vol. 3, pages 1-220 and references cited therein;“Comprehensive Heterocyclic Chemistry I”, Pergamon Press, 1984; vol. 4,pages 155-376 & vol. 5, pages 167-498 and references cited therein).

Subsequently, compounds (Ia) can be obtained by the reaction of (XVIII)with (XIX). If G stands for halogen, preferably chloride or bromide,compounds (XIX) are first transformed into Grignard reagents by thereaction with magnesium or with transmetallation reagents such asisopropylmagnesium halides and subsequently reacted with epoxides(XVIII) preferably under anhydrous conditions.

In an alternative route compounds (XIX) (G=hydrogen or halogen) arereacted with compounds (XVIII) preferably in the presence of a base.Compounds (XIX) (G=hydrogen or halogen) are optionally reacted with abase upfront, e.g. n-butyllithium, lithium-di-isopropylamide, lithiumbis(trimethylsilyl)amide, methyl lithium, followed by compounds of thegeneral structure (XVIII) preferably under anhydrous conditions to formthe desired compounds (Ia).

Process L (Scheme 12):

-   R²=C₁-C₈-alkyl, —Si(R^(3a))(R^(3b))(R^(3c)), —P(O)(OH)₂,    —CH₂—O—P(O)(OH)₂, substituted or non-substituted —C(O)—C₁-C₈-alkyl    or substituted, non-substituted —C(O)—C₃-C₇-cycloalkyl, substituted    or non-substituted —C(O)NH—C₁-C₈-alkyl; substituted or    non-substituted —C(O)N-di-C₁-C₈-alkyl; substituted or    non-substituted —C(O)O—C₁-C₈-alkyl

The compounds (Ia) obtained according to Processes H, I, J or K can beconverted by means of methods described in the literature to thecorresponding compounds (Ib) (see e.g. DE-A 3202604, JP-A 02101067, EP-A225 739, CN-A 101824002, FR-A 2802772). Compounds of the generalstructure (Ia) are preferably reacted with alkylhalides,dialkylsulfates, anhydrides, acid chlorides, phosphorylchloride oralkylisocyanate preferably in the presence of a base to obtain compounds(Ib).

General

The processes A to L according to the invention for preparing compoundsof the formula (I) are optionally performed using one or more reactionauxiliaries.

Useful reaction auxiliaries are, as appropriate, inorganic or organicbases or acid acceptors. These preferably include alkali metal oralkaline earth metal acetates, amides, carbonates, hydrogencarbonates,hydrides, hydroxides or alkoxides, for example sodium acetate, potassiumacetate or calcium acetate, lithium amide, sodium amide, potassium amideor calcium amide, sodium carbonate, potassium carbonate or calciumcarbonate, sodium hydrogencarbonate, potassium hydrogencarbonate orcalcium hydrogencarbonate, lithium hydride, sodium hydride, potassiumhydride or calcium hydride, lithium hydroxide, sodium hydroxide,potassium hydroxide or calcium hydroxide, n-butyllithium,sec-butyllithium, tert-butyllithium, lithium diisopropylamide, lithiumbis(trimethylsilyl)amide, sodium methoxide, ethoxide, n- or i-propoxide,n-, s- or t-butoxide or potassium methoxide, ethoxide, n- ori-propoxide, n-, i-, s- or t-butoxide; and also basic organic nitrogencompounds, for example trimethylamine, triethylamine, tripropylamine,tributylamine, ethyldiisopropylamine, N,N-dimethylcyclohexylamine,dicyclohexylamine, ethyldicyclohexylamine, N,N-dimethylaniline,N,N-dimethylbenzylamine, pyridine, 2-methyl-, 3-methyl-, 4-methyl-,2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and 3,5-dimethylpyridine,5-ethyl-2-methylpyridine, 4-dimethylaminopyridine, N-methylpiperidine,1,4-diazabicyclo[2.2.2]-octane (DABCO),1,5-diazabicyclo[4.3.0]-non-5-ene (DBN) or1,8-diazabicyclo[5.4.0]-undec-7-ene (DBU).

Useful reaction auxiliaries are, as appropriate, inorganic or organicacids. These preferably include inorganic acids, for example hydrogenfluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide,sulphuric acid, phosphoric acid and nitric acid, and acidic salts suchas NaHSO₄ and KHSO₄, or organic acids, for example, formic acid,carbonic acid and alkanoic acids such as acetic acid, trifluoroaceticacid, trichloroacetic acid and propionic acid, and also glycolic acid,thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid,cinnamic acid, oxalic acid, saturated or mono- or diunsaturated C₆-C₂₀fatty acids, alkylsulphuric monoesters, alkylsulphonic acids (sulphonicacids having straight-chain or branched alkyl radicals having 1 to 20carbon atoms), arylsulphonic acids or aryldisulphonic acids (aromaticradicals, such as phenyl and naphthyl, which bear one or two sulphonicacid groups), alkylphosphonic acids (phosphonic acids havingstraight-chain or branched alkyl radicals having 1 to 20 carbon atoms),arylphosphonic acids or aryldiphosphonic acids (aromatic radicals, suchas phenyl and naphthyl, which bear one or two phosphonic acid radicals),where the alkyl and aryl radicals may bear further substituents, forexample p-toluenesulphonic acid, salicylic acid, p-aminosalicylic acid,2-phenoxybenzoic acid, 2-acetoxybenzoic acid, etc.

The processes A to L according to the invention are optionally performedusing one or more diluents. Useful diluents are virtually all inertorganic solvents. Unless otherwise indicated for the above describedprocesses A to L, these preferably include aliphatic and aromatic,optionally halogenated hydrocarbons, such as pentane, hexane, heptane,cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene,xylene, methylene chloride, ethylene chloride, chloroform, carbontetrachloride, chlorobenzene and o-dichlorobenzene, ethers such asdiethyl ether, dibutyl ether and methyl tert-butyl ether, glycoldimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane,ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketoneand methyl isobutyl ketone, esters, such as methyl acetate and ethylacetate, nitriles, for example acetonitrile and propionitrile, amides,for example dimethylformamide, dimethylacetamide andN-methylpyrrolidone, and also dimethyl sulphoxide,tetramethylenesulphone and hexamethylphosphoramide and DMPU.

In the processes according to the invention, the reaction temperaturescan be varied within a relatively wide range. In general, thetemperatures employed are between −78° C. and 250° C., preferablytemperatures between −78° C. and 150° C.

The reaction time varies as a function of the scale of the reaction andof the reaction temperature, but is generally between a few minutes and48 hours.

The processes according to the invention are generally performed understandard pressure. However, it is also possible to work under elevatedor reduced pressure.

For performance of the processes according to the invention, thestarting materials required in each case are generally used inapproximately equimolar amounts. However, it is also possible to use oneof the components used in each case in a relatively large excess.

After a reaction has ended, the compounds are optionally separated fromthe reaction mixture by one of the customary separation techniques. Ifnecessary, the compounds are purified by recrystallization orchromatography.

If appropriate, in the processes A to L according to the invention alsosalts and/or N-oxides of the starting compounds can be used.

The invention further relates to novel intermediates of the compounds offormula (I), which form part of the invention.

Novel intermediates according to the present invention are novelcompounds of formula (V)

wherein

-   X represents a substituted or non-substituted 3-pyridinyl or    4-pyridinyl or a benzannulated derivative thereof;    and-   R¹ represents tert-butyl, 2-methyl-butan-2-yl; 3-methyl-pentan-3-yl    or 2,3-dimethyl-butan-2-yl    and its salts or N-oxides.

For compounds of formula (V) preferably

-   X represents a substituted or non-substituted 3-pyridinyl or    4-pyridinyl or a benzannulated derivative thereof;    and-   R¹ represents 2-methyl-butan-2-yl; 3-methyl-pentan-3-yl or    2,3-dimethyl-butan-2-yl.

For compounds of formula (V) also preferably

-   X represents a 3-pyridinyl or 4-pyridinyl substituted by at least    one halogen substituent or substituted or non-substituted    quinoline-2-yl or quinoline-3-yl;    and-   R¹ represents tert-butyl.

Further novel intermediates according to the present invention are novelepoxides of formula (XII)

wherein

-   X represents a substituted or non-substituted unsaturated 6-membered    heterocycle containing 1 or 2 nitrogen atom(s) as heteroatom(s) or a    benzannulated derivative thereof;    and-   R¹ represents substituted or non-substituted C₂-C₈-alkyl;    substituted or non-substituted C₄-C₈-cycloalkylalkyl; substituted or    non-substituted C₂-C₈-alkenyl; substituted or non-substituted    C₂-C₈-alkynyl;    and its salts or N-oxides.

Preferred radical definitions for X and R¹ have already been given abovefor the compounds of formula (I). Such preferred radical definitionsshall also apply for the epoxides of formula (XII).

Further novel intermediates according to the present invention are novelalcohols of formula (XV)

wherein

-   X represents a substituted or non-substituted unsaturated 6-membered    heterocycle containing 1 or 2 nitrogen atom(s) as heteroatom(s) or a    benzannulated derivative thereof;    and-   R¹ represents substituted or non-substituted C₁-C₈-alkyl;    substituted or non-substituted C₄-C₈-cycloalkylalkyl; substituted or    non-substituted C₂-C₈-alkenyl; substituted or non-substituted    C₂-C₈-alkynyl;    and-   A represents chlorine, bromine, iodine, O—SO₂—C₁-C₈-alkyl or    O—SO₂-aryl, preferably chlorine or bromine;    and its salts or N-oxides. Preferred radical definitions for X and    R¹ have already been given above for the compounds of formula (I).    Such preferred radical definitions shall also apply for the alcohols    of formula (XV).

The compounds of the formula (I) according to the invention can beconverted into physiologically acceptable salts, e.g. as acid additionsalts or metal salt complexes.

Depending on the nature of the substituents defined above, the compoundsof the formula (I) have acidic or basic properties and can form salts,if appropriate also inner salts, or adducts with inorganic or organicacids or with bases or with metal ions. If the compounds of the formula(I) carry amino, alkylamino or other groups which induce basicproperties, these compounds can be reacted with acids to give salts, orthey are directly obtained as salts in the synthesis. If the compoundsof the formula (I) carries hydroxyl, carboxyl or other groups whichinduce acidic properties, these compounds can be reacted with bases togive salts. Suitable bases are, for example, hydroxides, carbonates,bicarbonates of the alkali metals and alkaline earth metals, inparticular those of sodium, potassium, magnesium and calcium,furthermore ammonia, primary, secondary and tertiary amines having(C₁-C₄)-alkyl groups, mono-, di- and trialkanolamines of(C₁-C₄)-alkanols, choline and also chlorocholine.

The salts obtainable in this manner also have fungicidal properties.

Examples of inorganic acids are hydrohalic acids, such as hydrogenfluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide,sulphuric acid, phosphoric acid and nitric acid, and acidic salts, suchas NaHSO₄ and KHSO₄. Suitable organic acids are, for example, formicacid, carbonic acid and alkanoic acids, such as acetic acid,trifluoroacetic acid, trichloroacetic acid and propionic acid, and alsoglycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid,benzoic acid, cinnamic acid, maleic acid, fumaric acid, tartaric acid,sorbic acid oxalic acid, alkylsulphonic acids (sulphonic acids havingstraight-chain or branched alkyl radicals of 1 to 20 carbon atoms),arylsulphonic acids or aryldisulphonic acids (aromatic radicals, such asphenyl and naphthyl, which carry one or two sulphonic acid groups),alkylphosphonic acids (phosphonic acids having straight-chain orbranched alkyl radicals of 1 to 20 carbon atoms), arylphosphonic acidsor aryldiphosphonic acids (aromatic radicals, such as phenyl andnaphthyl, which carry one or two phosphonic acid radicals), where thealkyl and aryl radicals may carry further substituents, for examplep-toluenesulphonic acid, 1,5-naphthalenedisulphonic acid, salicylicacid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoicacid, etc.

Suitable metal ions are in particular the ions of the elements of thesecond main group, in particular calcium and magnesium, of the third andfourth main group, in particular aluminium, tin and lead, and also ofthe first to eighth transition group, in particular chromium, manganese,iron, cobalt, nickel, copper, zinc and others. Particular preference isgiven to the metal ions of the elements of the fourth period. Here, themetals can be present in various valencies that they can assume.

The acid addition salts of the compounds of the formula (I) can beobtained in a simple manner by customary methods for forming salts, forexample by dissolving a compound of the formula (I) in a suitable inertsolvent and adding the acid, for example hydrochloric acid, and beisolated in a known manner, for example by filtration, and, if required,be purified by washing with an inert organic solvent.

Suitable anions of the salts are those which are preferably derived fromthe following acids: hydrohalic acids, such as, for example,hydrochloric acid and hydrobromic acid, furthermore phosphoric acid,nitric acid and sulphuric acid.

The metal salt complexes of compounds of the formula (I) can be obtainedin a simple manner by customary processes, for example by dissolving themetal salt in alcohol, for example ethanol, and adding the solution tothe compound of the formula (I). Metal salt complexes can be isolated ina known manner, for example by filtration, and, if required, be purifiedby recrystallization.

Salts of the intermediates can also be prepared according to theprocesses mentioned above for the salts of compounds of formula (I).

N-oxides of compounds of the formula (I) or intermediates thereof can beobtained in a simple manner by customary processes, for example byN-oxidation with hydrogen peroxide (H₂O₂), peracids, for example peroxysulfuric acid or peroxy carboxylic acids, such asmeta-chloroperoxybenzoic acid or peroxymonosulfuric acid (Caro's acid).

Composition/Formulation

The present invention further relates to a crop protection compositionfor controlling harmful microorganisms, especially unwanted fungi andbacteria, comprising an effective and non-phytotoxic amount of theinventive active ingredients. These are preferably fungicidalcompositions which comprise agriculturally suitable auxiliaries,solvents, carriers, surfactants or extenders.

In the context of the present invention, “control of harmfulmicroorganisms” means a reduction in infestation by harmfulmicroorganisms, compared with the untreated plant measured as fungicidalefficacy, preferably a reduction by 25-50%, compared with the untreatedplant (100%), more preferably a reduction by 40-79%, compared with theuntreated plant (100%); even more preferably, the infection by harmfulmicroorganisms is entirely suppressed (by 70-100%). The control may becurative, i.e. for treatment of already infected plants, or protective,for protection of plants which have not yet been infected.

An “effective but non-phytotoxic amount” means an amount of theinventive composition which is sufficient to control the fungal diseaseof the plant in a satisfactory manner or to eradicate the fungal diseasecompletely, and which, at the same time, does not cause any significantsymptoms of phytotoxicity. In general, this application rate may varywithin a relatively wide range. It depends on several factors, forexample on the fungus to be controlled, the plant, the climaticconditions and the ingredients of the inventive compositions.

Suitable organic solvents include all polar and non-polar organicsolvents usually employed for formulation purposes. Preferable thesolvents are selected from ketones, e.g. methyl-isobutyl-ketone andcyclohexanone, amides, e.g. dimethyl formamide and alkanecarboxylic acidamides, e.g. N,N-dimethyl decaneamide and N,N-dimethyl octanamide,furthermore cyclic solvents, e.g. N-methyl-pyrrolidone,N-octyl-pyrrolidone, N-dodecyl-pyrrolidone, N-octyl-caprolactame,N-dodecyl-caprolactame and butyrolactone, furthermore strong polarsolvents, e.g. dimethylsulfoxide, and aromatic hydrocarbons, e.g. xylol,Solvesso™, mineral oils, e.g. white spirit, petroleum, alkyl benzenesand spindle oil, also esters, e.g. propyleneglycol-monomethyletheracetate, adipic acid dibutylester, acetic acid hexylester, acetic acidheptylester, citric acid tri-n-butylester and phthalic aciddi-n-butylester, and also alcohols, e.g. benzyl alcohol and1-methoxy-2-propanol.

According to the invention, a carrier is a natural or synthetic, organicor inorganic substance with which the active ingredients are mixed orcombined for better applicability, in particular for application toplants or plant parts or seed. The carrier, which may be solid orliquid, is generally inert and should be suitable for use inagriculture.

Useful solid or liquid carriers include: for example ammonium salts andnatural rock dusts, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and synthetic rockdusts, such as finely divided silica, alumina and natural or syntheticsilicates, resins, waxes, solid fertilizers, water, alcohols, especiallybutanol, organic solvents, mineral and vegetable oils, and derivativesthereof. Mixtures of such carriers can likewise be used.

Suitable solid filler and carrier include inorganic particles, e.g.carbonates, silikates, sulphates and oxides with an average particlesize of between 0.005 and 20 μm, preferably of between 0.02 to 10 μm,for example ammonium sulphate, ammonium phosphate, urea, calciumcarbonate, calcium sulphate, magnesium sulphate, magnesium oxide,aluminium oxide, silicium dioxide, so-called fine-particle silica,silica gels, natural or synthetic silicates, and alumosilicates andplant products like cereal flour, wood powder/sawdust and cellulosepowder.

Useful solid carriers for granules include: for example crushed andfractionated natural rocks such as calcite, marble, pumice, sepiolite,dolomite, and synthetic granules of inorganic and organic meals, andalso granules of organic material such as sawdust, coconut shells, maizecobs and tobacco stalks.

Useful liquefied gaseous extenders or carriers are those liquids whichare gaseous at standard temperature and under standard pressure, forexample aerosol propellants such as halohydrocarbons, and also butane,propane, nitrogen and carbon dioxide.

In the formulations, it is possible to use tackifiers such ascarboxymethylcellulose, and natural and synthetic polymers in the formof powders, granules or latices, such as gum arabic, polyvinyl alcoholand polyvinyl acetate, or else natural phospholipids, such as cephalinsand lecithins, and synthetic phospholipids. Further additives may bemineral and vegetable oils.

If the extender used is water, it is also possible to employ, forexample, organic solvents as auxiliary solvents. Useful liquid solventsare essentially: aromatics such as xylene, toluene or alkylnaphthalenes,chlorinated aromatics and chlorinated aliphatic hydrocarbons such aschlorobenzenes, chloroethylenes or dichloromethane, aliphatichydrocarbons such as cyclohexane or paraffins, for example mineral oilfractions, mineral and vegetable oils, alcohols such as butanol orglycol and their ethers and esters, ketones such as acetone, methylethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polarsolvents such as dimethylformamide and dimethyl sulphoxide, and alsowater.

Suitable surfactants (adjuvants, emulsifiers, dispersants, protectivecolloids, wetting agent and adhesive) include all common ionic andnon-ionic substances, for example ethoxylated nonylphenols, polyalkyleneglycolether of linear or branched alcohols, reaction products of alkylphenols with ethylene oxide and/or propylene oxide, reaction products offatty acid amines with ethylene oxide and/or propylene oxide,furthermore fattic acid esters, alkyl sulfonates, alkyl sulphates, alkylethersulphates, alkyl etherphosphates, arylsulphate, ethoxylatedarylalkylphenols, e.g. tristyryl-phenol-ethoxylates, furthermoreethoxylated and propoxylated arylalkylphenols like sulphated orphosphated arylalkylphenol-ethoxylates and -ethoxy- and -propoxylates.Further examples are natural and synthetic, water soluble polymers, e.g.lignosulphonates, gelatine, gum arabic, phospholipides, starch,hydrophobic modified starch and cellulose derivatives, in particularcellulose ester and cellulose ether, further polyvinyl alcohol,polyvinyl acetate, polyvinyl pyrrolidone, polyacrylic acid,polymethacrylic acid and co-polymerisates of (meth)acrylic acid and(meth)acrylic acid esters, and further co-polymerisates of methacrylicacid and methacrylic acid esters which are neutralized with alkalimetalhydroxide and also condensation products of optionally substitutednaphthalene sulfonic acid salts with formaldehyde. The presence of asurfactant is necessary if one of the active ingredients and/or one ofthe inert carriers is insoluble in water and when application iseffected in water. The proportion of surfactants is between 5 and 40percent by weight of the inventive composition.

It is possible to use dyes such as inorganic pigments, for example ironoxide, titanium oxide and Prussian Blue, and organic dyes such asalizarin dyes, azo dyes and metal phthalocyanine dyes, and tracenutrients such as salts of iron, manganese, boron, copper, cobalt,molybdenum and zinc.

Antifoams which may be present in the formulations include e.g. siliconeemulsions, longchain alcohols, fatty acids and their salts as well asfluoroorganic substances and mixtures thereof.

Examples of thickeners are polysaccharides, e.g. xanthan gum or veegum,silicates, e.g. attapulgite, bentonite as well as fine-particle silica.

If appropriate, it is also possible for other additional components tobe present, for example protective colloids, binders, adhesives,thickeners, thixotropic substances, penetrants, stabilizers,sequestrants, complexing agents. In general, the active ingredients canbe combined with any solid or liquid additive commonly used forformulation purposes.

The inventive active ingredients or compositions can be used as such or,depending on their particular physical and/or chemical properties, inthe form of their formulations or the use forms prepared therefrom, suchas aerosols, capsule suspensions, cold-fogging concentrates,warm-fogging concentrates, encapsulated granules, fine granules,flowable concentrates for the treatment of seed, ready-to-use solutions,dustable powders, emulsifiable concentrates, oil-in-water emulsions,water-in-oil emulsions, macrogranules, microgranules, oil-dispersiblepowders, oil-miscible flowable concentrates, oil-miscible liquids, gas(under pressure), gas generating product, foams, pastes, pesticidecoated seed, suspension concentrates, suspoemulsion concentrates,soluble concentrates, suspensions, wettable powders, soluble powders,dusts and granules, water-soluble and water-dispersible granules ortablets, water-soluble and water-dispersible powders for the treatmentof seed, wettable powders, natural products and synthetic substancesimpregnated with active ingredient, and also microencapsulations inpolymeric substances and in coating materials for seed, and also ULVcold-fogging and warm-fogging formulations.

The inventive compositions include not only formulations which arealready ready for use and can be applied with a suitable apparatus tothe plant or the seed, but also commercial concentrates which have to bediluted with water prior to use. Customary applications are for exampledilution in water and subsequent spraying of the resulting spray liquor,application after dilution in oil, direct application without dilution,seed treatment or soil application of granules.

The inventive compositions and formulations generally contain between0.05 and 99% by weight, 0.01 and 98% by weight, preferably between 0.1and 95% by weight, more preferably between 0.5 and 90% of activeingredient, most preferably between 10 and 70% by weight. For specialapplications, e.g. for protection of wood and derived timber productsthe inventive compositions and formulations generally contain between0.0001 and 95% by weight, preferably 0.001 to 60% by weight of activeingredient.

The contents of active ingredient in the application forms prepared fromthe commercial formulations may vary in a broad range. The concentrationof the active ingredients in the application forms is generally between0.000001 to 95% by weight, preferably between 0.0001 and 2% by weight.

The formulations mentioned can be prepared in a manner known per se, forexample by mixing the active ingredients with at least one customaryextender, solvent or diluent, adjuvant, emulsifier, dispersant, and/orbinder or fixative, wetting agent, water repellent, if appropriatedesiccants and UV stabilizers and, if appropriate, dyes and pigments,antifoams, preservatives, inorganic and organic thickeners, adhesives,gibberellins and also further processing auxiliaries and also water.Depending on the formulation type to be prepared further processingsteps are necessary, e.g. wet grinding, dry grinding and granulation.The inventive active ingredients may be present as such or in their(commercial) formulations and in the use forms prepared from theseformulations as a mixture with other (known) active ingredients, such asinsecticides, attractants, sterilants, bactericides, acaricides,nematicides, fungicides, growth regulators, herbicides, fertilizers,safeners and/or semiochemicals.

The inventive treatment of the plants and plant parts with the activeingredients or compositions is effected directly or by action on theirsurroundings, habitat or storage space by the customary treatmentmethods, for example by dipping, spraying, atomizing, irrigating,evaporating, dusting, fogging, broadcasting, foaming, painting,spreading-on, watering (drenching), drip irrigating and, in the case ofpropagation material, especially in the case of seeds, also by dry seedtreatment, wet seed treatment, slurry treatment, incrustation, coatingwith one or more coats, etc. It is also possible to deploy the activeingredients by the ultra-low volume method or to inject the activeingredient preparation or the active ingredient itself into the soil.

Plant/Crop Protection

The inventive active ingredients or compositions have potentmicrobicidal activity and can be used for control of unwantedmicroorganisms, such as fungi and bacteria, in crop protection and inthe protection of materials.

The invention also relates to a method for controlling unwantedmicroorganisms, characterized in that the inventive active ingredientsare applied to the phytopathogenic fungi, phytopathogenic bacteriaand/or their habitat.

Fungicides can be used in crop protection for control of phytopathogenicfungi. They are characterized by an outstanding efficacy against a broadspectrum of phytopathogenic fungi, including soilborne pathogens, whichare in particular members of the classes Plasmodiophoromycetes,Peronosporomycetes (Syn. Oomycetes), Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes (Syn. Fungi impeifecti).Some fungicides are systemically active and ca be used in plantprotection as foliar, seed dressing or soil fungicide. Furthermore, theyare suitable for combating fungi, which inter alia infest wood or rootsof plant.

Bactericides can be used in crop protection for control ofPseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceaeand Streptomycetaceae.

Non-limiting examples of pathogens of fungal diseases which can betreated in accordance with the invention include:

diseases caused by powdery mildew pathogens, for example Blumeriaspecies, for example Blumeria graminis; Podosphaera species, for examplePodosphaera leucotricha; Sphaerotheca species, for example Sphaerothecafuliginea; Uncinula species, for example Uncinula necator;diseases caused by rust disease pathogens, for example Gymnosporangiumspecies, for example Gymnosporangium sabinae; Hemileia species, forexample Hemileia vastatrix; Phakopsora species, for example Phakopsorapachyrhizi and Phakopsora meibomiae; Puccinia species, for examplePuccinia recondite, P. triticina, P. graminis or P. striiformis;Uromyces species, for example Uromyces appendiculatus;diseases caused by pathogens from the group of the Oomycetes, forexample Albugo species, for example Algubo candida; Bremia species, forexample Bremia lactucae; Peronospora species, for example Peronosporapisi or P. brassicae; Phytophthora species, for example Phytophthorainfestans; Plasmopara species, for example Plasmopara viticola;Pseudoperonospora species, for example Pseudoperonospora humuli orPseudoperonospora cubensis; Pythium species, for example Pythiumultimum;leaf blotch diseases and leaf wilt diseases caused, for example, byAlternaria species, for example Alternaria solani; Cercospora species,for example Cercospora beticola; Cladiosporium species, for exampleCladiosporium cucumerinum; Cochliobolus species, for exampleCochliobolus sativus (conidia form: Drechslera, Syn: Helminthosporium),Cochliobolus miyabeanus; Colletotrichum species, for exampleColletotrichum lindemuthanium; Cycloconium species, for exampleCycloconium oleaginum; Diaporthe species, for example Diaporthe citri;Elsinoe species, for example Elsinoe fawcettii; Gloeosporium species,for example Gloeosporium laeticolor; Glomerella species, for exampleGlomerella cingulata; Guignardia species, for example Guignardiabidwelli; Leptosphaeria species, for example Leptosphaeria maculans,Leptosphaeria nodorum; Magnaporthe species, for example Magnaporthegrisea; Microdochium species, for example Microdochium nivale;Mycosphaerella species, for example Mycosphaerella graminicola, M.arachidicola and M. fijiensis; Phaeosphaeria species, for examplePhaeosphaeria nodorum; Pyrenophora species, for example Pyrenophorateres, Pyrenophora tritici repentis; Ramularia species, for exampleRamularia collo-cygni, Ramularia areola; Rhynchosporium species, forexample Rhynchosporium secalis; Septoria species, for example Septoriaapii, Septoria lycopersii; Typhula species, for example Typhulaincarnate; Venturia species, for example Venturia inaequalis;root and stem diseases caused, for example, by Corticium species, forexample Corticium graminearum; Fusarium species, for example Fusariumoxysporum; Gaeumannomyces species, for example Gaeumannomyces graminis;Rhizoctonia species, such as, for example Rhizoctonia solani;Sarocladium diseases caused for example by Sarocladium oryzae;Sclerotium diseases caused for example by Sclerotium oryzae; Tapesiaspecies, for example Tapesia acuformis; Thielaviopsis species, forexample Thielaviopsis basicola;ear and panicle diseases (including corn cobs) caused, for example, byAlternaria species, for example Alternaria spp.; Aspergillus species,for example Aspergillus flavus; Cladosporium species, for exampleCladosporium cladosporioides; Claviceps species, for example Clavicepspurpurea; Fusarium species, for example Fusarium culmorum; Gibberellaspecies, for example Gibberella zeae; Monographella species, for exampleMonographella nivalis; Septoria species, for example Septoria nodorum;diseases caused by smut fungi, for example Sphacelotheca species, forexample Sphacelotheca reiliana; Tilletia species, for example Tilletiacaries, T. controversa; Urocystis species, for example Urocystisocculta; Ustilago species, for example Ustilago nuda, U. nuda tritici;fruit rot caused, for example, by Aspergillus species, for exampleAspergillus flavus; Botrytis species, for example Botrytis cinerea;Penicillium species, for example Penicillium expansum and P.purpurogenum; Sclerotinia species, for example Sclerotinia sclerotiorum;Verticilium species, for example Verticilium alboatrum;seed and soilborne decay, mould, wilt, rot and damping-off diseasescaused, for example, by Alternaria species, caused for example byAlternaria brassicicola; Aphanomyces species, caused for example byAphanomyces euteiches; Ascochyta species, caused for example byAscochyta lentis; Aspergillus species, caused for example by Aspergillusflavus; Cladosporium species, caused for example by Cladosporiumherbarum; Cochliobolus species, caused for example by Cochliobolussativus; (Conidiaform: Drechslera, Bipolaris Syn: Helminthosporium);Colletotrichum species, caused for example by Colletotrichum coccodes;Fusarium species, caused for example by Fusarium culmorum; Gibberellaspecies, caused for example by Gibberella zeae; Macrophomina species,caused for example by Macrophomina phaseolina; Monographella species,caused for example by Monographella nivalis; Penicillium species, causedfor example by Penicillium expansum; Phoma species, caused for exampleby Phoma lingam; Phomopsis species, caused for example by Phomopsissojae; Phytophthora species, caused for example by Phytophthoracactorum; Pyrenophora species, caused for example by Pyrenophoragraminea; Pyricularia species, caused for example by Pyricularia oryzae;Pythium species, caused for example by Pythium ultimum; Rhizoctoniaspecies, caused for example by Rhizoctonia solani; Rhizopus species,caused for example by Rhizopus oryzae; Sclerotium species, caused forexample by Sclerotium rolfsii; Septoria species, caused for example bySeptoria nodorum; Typhula species, caused for example by Typhulaincarnata; Verticillium species, caused for example by Verticilliumdahliae;cancers, galls and witches' broom caused, for example, by Nectriaspecies, for example Nectria galligena;wilt diseases caused, for example, by Monilinia species, for exampleMonilinia laxa;leaf blister or leaf curl diseases caused, for example, by Exobasidiumspecies, for example Exobasidium vexans; Taphrina species, for exampleTaphrina deformans;decline diseases of wooden plants caused, for example, by Esca disease,caused for example by Phaemoniella clamydospora, Phaeoacremoniumaleophilum and Fomitiporia mediterranea; Eutypa dyeback, caused forexample by Eutypa lata; Ganoderma diseases caused for example byGanoderma boninense; Rigidoporus diseases caused for example byRigidoporus lignosus;diseases of flowers and seeds caused, for example, by Botrytis species,for example Botrytis cinerea;diseases of plant tubers caused, for example, by Rhizoctonia species,for example Rhizoctonia solani; Helminthosporium species, for exampleHelminthosporium solani;Club root caused, for example, by Plasmodiophora species, for examplePlamodiophora brassicae; diseases caused by bacterial pathogens, forexample Xanthomonas species, for example Xanthomonas campestris pv.oryzae; Pseudomonas species, for example Pseudomonas syringae pv.lachrymans; Erwinia species, for example Erwinia amylovora.

The following diseases of soya beans can be controlled with preference:

Fungal diseases on leaves, stems, pods and seeds caused, for example, byAlternaria leaf spot (Alternaria spec. atrans tenuissima), Anthracnose(Colletotrichum gloeosporoides dematium var. truncatum), brown spot(Septoria glycines), cercospora leaf spot and blight (Cercosporakikuchii), choanephora leaf blight (Choanephora infundibulifera trispora(Syn.)), dactuliophora leaf spot (Dactuliophora glycines), downy mildew(Peronospora manshurica), drechslera blight (Drechslera glycini),frogeye leaf spot (Cercospora sojina), leptosphaerulina leaf spot(Leptosphaerulina trifolii), phyllostica leaf spot (Phyllostictasojaecola), pod and stem blight (Phomopsis sojae), powdery mildew(Microsphaera diffusa), pyrenochaeta leaf spot (Pyrenochaeta glycines),rhizoctonia aerial, foliage, and web blight (Rhizoctonia solani), rust(Phakopsora pachyrhizi, Phakopsora meibomiae), scab (Sphacelomaglycines), stemphylium leaf blight (Stemphylium botryosum), target spot(Corynespora cassiicola).

Fungal diseases on roots and the stem base caused, for example, by blackroot rot (Calonectria crotalariae), charcoal rot (Macrophominaphaseolina), fusarium blight or wilt, root rot, and pod and collar rot(Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusariumequiseti), mycoleptodiscus root rot (Mycoleptodiscus terrestris),neocosmospora (Neocosmospora vasinfecta), pod and stem blight (Diaporthephaseolorum), stem canker (Diaporthe phaseolorum var. caulivora),phytophthora rot (Phytophthora megasperma), brown stem rot (Phialophoragregata), pythium rot (Pythium aphanidermatum, Pythium irregulare,Pythium debaryanum, Pythium myriotylum, Pythium ultimum), rhizoctoniaroot rot, stem decay, and damping-off (Rhizoctonia solani), sclerotiniastem decay (Sclerotinia sclerotiorum), sclerotinia southern blight(Sclerotinia rolfsii), thielaviopsis root rot (Thielaviopsis basicola).

The inventive fungicidal compositions can be used for curative orprotective/preventive control of phytopathogenic fungi. The inventiontherefore also relates to curative and protective methods forcontrolling phytopathogenic fungi by the use of the inventive activeingredients or compositions, which are applied to the seed, the plant orplant parts, the fruit or the soil in which the plants grow.

The fact that the active ingredients are well tolerated by plants at theconcentrations required for controlling plant diseases allows thetreatment of above-ground parts of plants, of propagation stock andseeds, and of the soil.

According to the invention all plants and plant parts can be treated. Byplants is meant all plants and plant populations such as desirable andundesirable wild plants, cultivars and plant varieties (whether or notprotectable by plant variety or plant breeder's rights). Cultivars andplant varieties can be plants obtained by conventional propagation andbreeding methods which can be assisted or supplemented by one or morebiotechnological methods such as by use of double haploids, protoplastfusion, random and directed mutagenesis, molecular or genetic markers orby bioengineering and genetic engineering methods. By plant parts ismeant all above ground and below ground parts and organs of plants suchas shoot, leaf, blossom and root, whereby for example leaves, needles,stems, branches, blossoms, fruiting bodies, fruits and seed as well asroots, corms and rhizomes are listed. Crops and vegetative andgenerative propagating material, for example cuttings, corms, rhizomes,runners and seeds also belong to plant parts.

The inventive active ingredients, when they are well tolerated byplants, have favourable homeotherm toxicity and are well tolerated bythe environment, are suitable for protecting plants and plant organs,for enhancing harvest yields, for improving the quality of the harvestedmaterial. They can preferably be used as crop protection compositions.They are active against normally sensitive and resistant species andagainst all or some stages of development.

Plants which can be treated in accordance with the invention include thefollowing main crop plants: maize, soya bean, alfalfa, cotton,sunflower, Brassica oil seeds such as Brassica napus (e.g. canola,rapeseed), Brassica rapa, B. juncea (e.g. (field) mustard) and Brassicacarinata, Arecaceae sp. (e.g. oilpalm, coconut), rice, wheat, sugarbeet, sugar cane, oats, rye, barley, millet and sorghum, triticale,flax, nuts, grapes and vine and various fruit and vegetables fromvarious botanic taxa, e.g. Rosaceae sp. (e.g. pome fruits such as applesand pears, but also stone fruits such as apricots, cherries, almonds,plums and peaches, and berry fruits such as strawberries, raspberries,red and black currant and gooseberry), Ribesioidae sp., Juglandaceaesp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp.,Oleaceae sp. (e.g. olive tree), Actinidaceae sp., Lauraceae sp. (e.g.avocado, cinnamon, camphor), Musaceae sp. (e.g. banana trees andplantations), Rubiaceae sp. (e.g. coffee), Theaceae sp. (e.g. tea),Sterculiceae sp., Rutaceae sp. (e.g. lemons, oranges, mandarins andgrapefruit); Solanaceae sp. (e.g. tomatoes, potatoes, peppers, capsicum,aubergines, tobacco), Liliaceae sp., Compositae sp. (e.g. lettuce,artichokes and chicory—including root chicory, endive or commonchicory), Umbelliferae sp. (e.g. carrots, parsley, celery and celeriac),Cucurbitaceae sp. (e.g. cucumbers—including gherkins, pumpkins,watermelons, calabashes and melons), Alliaceae sp. (e.g. leeks andonions), Cruciferae sp. (e.g. white cabbage, red cabbage, broccoli,cauliflower, Brussels sprouts, pak choi, kohlrabi, radishes,horseradish, cress and chinese cabbage), Leguminosae sp. (e.g. peanuts,peas, lentils and beans—e.g. common beans and broad beans),Chenopodiaceae sp. (e.g. Swiss chard, fodder beet, spinach, beetroot),Linaceae sp. (e.g. hemp), Cannabeacea sp. (e.g. cannabis), Malvaceae sp.(e.g. okra, cocoa), Papaveraceae (e.g. poppy), Asparagaceae (e.g.asparagus); useful plants and ornamental plants in the garden and woodsincluding turf, lawn, grass and Stevia rebaudiana; and in each casegenetically modified types of these plants.

Plant Growth Regulation

In some cases, the inventive compounds can, at particular concentrationsor application rates, also be used as herbicides, safeners, growthregulators or agents to improve plant properties, or as microbicides,for example as fungicides, antimycotics, bactericides, viricides(including compositions against viroids) or as compositions against MLO(Mycoplasma-like organisms) and RLO (Rickettsia-like organisms). Ifappropriate, they can also be used as intermediates or precursors forthe synthesis of other active ingredients.

The inventive active ingredients intervene in the metabolism of theplants and can therefore also be used as growth regulators.

Plant growth regulators may exert various effects on plants. The effectof the substances depends essentially on the time of application inrelation to the developmental stage of the plant, and also on theamounts of active ingredient applied to the plants or their environmentand on the type of application. In each case, growth regulators shouldhave a particular desired effect on the crop plants.

Plant growth-regulating compounds can be used, for example, to inhibitthe vegetative growth of the plants. Such inhibition of growth is ofeconomic interest, for example, in the case of grasses, since it is thuspossible to reduce the frequency of grass cutting in ornamental gardens,parks and sport facilities, on roadsides, at airports or in fruit crops.Also of significance is the inhibition of the growth of herbaceous andwoody plants on roadsides and in the vicinity of pipelines or overheadcables, or quite generally in areas where vigorous plant growth isunwanted.

Also important is the use of growth regulators for inhibition of thelongitudinal growth of cereal. This reduces or completely eliminates therisk of lodging of the plants prior to harvest. In addition, growthregulators in the case of cereals can strengthen the culm, which alsocounteracts lodging. The employment of growth regulators for shorteningand strengthening culms allows the deployment of higher fertilizervolumes to increase the yield, without any risk of lodging of the cerealcrop.

In many crop plants, inhibition of vegetative growth allows denserplanting, and it is thus possible to achieve higher yields based on thesoil surface. Another advantage of the smaller plants obtained in thisway is that the crop is easier to cultivate and harvest.

Inhibition of the vegetative plant growth may also lead to enhancedyields because the nutrients and assimilates are of more benefit toflower and fruit formation than to the vegetative parts of the plants.

Frequently, growth regulators can also be used to promote vegetativegrowth. This is of great benefit when harvesting the vegetative plantparts. However, promoting vegetative growth may also promote generativegrowth in that more assimilates are formed, resulting in more or largerfruits.

In some cases, yield increases may be achieved by manipulating themetabolism of the plant, without any detectable changes in vegetativegrowth. In addition, growth regulators can be used to alter thecomposition of the plants, which in turn may result in an improvement inquality of the harvested products. For example, it is possible toincrease the sugar content in sugar beet, sugar cane, pineapples and incitrus fruit, or to increase the protein content in soya or cereals. Itis also possible, for example, to use growth regulators to inhibit thedegradation of desirable ingredients, for example sugar in sugar beet orsugar cane, before or after harvest. It is also possible to positivelyinfluence the production or the elimination of secondary plantingredients. One example is the stimulation of the flow of latex inrubber trees.

Under the influence of growth regulators, parthenocarpic fruits may beformed. In addition, it is possible to influence the sex of the flowers.It is also possible to produce sterile pollen, which is of greatimportance in the breeding and production of hybrid seed.

Use of growth regulators can control the branching of the plants. On theone hand, by breaking apical dominance, it is possible to promote thedevelopment of side shoots, which may be highly desirable particularlyin the cultivation of ornamental plants, also in combination with aninhibition of growth. On the other hand, however, it is also possible toinhibit the growth of the side shoots. This effect is of particularinterest, for example, in the cultivation of tobacco or in thecultivation of tomatoes.

Under the influence of growth regulators, the amount of leaves on theplants can be controlled such that defoliation of the plants is achievedat a desired time. Such defoliation plays a major role in the mechanicalharvesting of cotton, but is also of interest for facilitatingharvesting in other crops, for example in viticulture. Defoliation ofthe plants can also be undertaken to lower the transpiration of theplants before they are transplanted.

Growth regulators can likewise be used to regulate fruit dehiscence. Onthe one hand, it is possible to prevent premature fruit dehiscence. Onthe other hand, it is also possible to promote fruit dehiscence or evenflower abortion to achieve a desired mass (“thinning”), in order toeliminate alternation. Alternation is understood to mean thecharacteristic of some fruit species, for endogenous reasons, to deliververy different yields from year to year Finally, it is possible to usegrowth regulators at the time of harvest to reduce the forces requiredto detach the fruits, in order to allow mechanical harvesting or tofacilitate manual harvesting.

Growth regulators can also be used to achieve faster or else delayedripening of the harvested material before or after harvest. This isparticularly advantageous as it allows optimal adjustment to therequirements of the market. Moreover, growth regulators in some casescan improve the fruit colour. In addition, growth regulators can also beused to concentrate maturation within a certain period of time. Thisestablishes the prerequisites for complete mechanical or manualharvesting in a single operation, for example in the case of tobacco,tomatoes or coffee.

By using growth regulators, it is additionally possible to influence theresting of seed or buds of the plants, such that plants such aspineapple or ornamental plants in nurseries, for example, germinate,sprout or flower at a time when they are normally not inclined to do so.In areas where there is a risk of frost, it may be desirable to delaybudding or germination of seeds with the aid of growth regulators, inorder to avoid damage resulting from late frosts.

Finally, growth regulators can induce resistance of the plants to frost,drought or high salinity of the soil. This allows the cultivation ofplants in regions which are normally unsuitable for this purpose.

Resistance Induction/Plant Health and Other Effects

The active compounds according to the invention also exhibit a potentstrengthening effect in plants. Accordingly, they can be used formobilizing the defences of the plant against attack by undesirablemicroorganisms.

Plant-strengthening (resistance-inducing) substances are to beunderstood as meaning, in the present context, those substances whichare capable of stimulating the defence system of plants in such a waythat the treated plants, when subsequently inoculated with undesirablemicroorganisms, develop a high degree of resistance to thesemicroorganisms.

The active compounds according to the invention are also suitable forincreasing the yield of crops. In addition, they show reduced toxicityand are well tolerated by plants.

Further, in context with the present invention plant physiology effectscomprise the following:

Abiotic stress tolerance, comprising temperature tolerance, droughttolerance and recovery after drought stress, water use efficiency(correlating to reduced water consumption), flood tolerance, ozonestress and UV tolerance, tolerance towards chemicals like heavy metals,salts, pesticides (safener) etc.Biotic stress tolerance, comprising increased fungal resistance andincreased resistance against nematodes, viruses and bacteria. In contextwith the present invention, biotic stress tolerance preferably comprisesincreased fungal resistance and increased resistance against nematodesIncreased plant vigor, comprising plant health/plant quality and seedvigor, reduced stand failure, improved appearance, increased recovery,improved greening effect and improved photosynthetic efficiency.

Effects on plant hormones and/or functional enzymes.

Effects on growth regulators (promoters), comprising earliergermination, better emergence, more developed root system and/orimproved root growth, increased ability of tillering, more productivetillers, earlier flowering, increased plant height and/or biomass,shorting of stems, improvements in shoot growth, number of kernels/ear,number of ears/m², number of stolons and/or number of flowers, enhancedharvest index, bigger leaves, less dead basal leaves, improvedphyllotaxy, earlier maturation/earlier fruit finish, homogenous riping,increased duration of grain filling, better fruit finish, biggerfruit/vegetable size, sprouting resistance and reduced lodging.

Increased yield, referring to total biomass per hectare, yield perhectare, kernel/fruit weight, seed size and/or hectoliter weight as wellas to increased product quality, comprising:

improved processability relating to size distribution (kernel, fruit,etc.), homogenous riping, grain moisture, better milling, bettervinification, better brewing, increased juice yield, harvestability,digestibility, sedimentation value, falling number, pod stability,storage stability, improved fiber length/strength/uniformity, increaseof milk and/or meet quality of silage fed animals, adaptation to cookingand frying;further comprising improved marketability relating to improvedfruit/grain quality, size distribution (kernel, fruit, etc.), increasedstorage/shelf-life, firmness/softness, taste (aroma, texture, etc.),grade (size, shape, number of berries, etc.), number of berries/fruitsper bunch, crispness, freshness, coverage with wax, frequency ofphysiological disorders, colour, etc.;further comprising increased desired ingredients such as e.g. proteincontent, fatty acids, oil content, oil quality, aminoacid composition,sugar content, acid content (pH), sugar/acid ratio (Brix), polyphenols,starch content, nutritional quality, gluten content/index, energycontent, taste, etc.;and further comprising decreased undesired ingredients such as e.g. lessmycotoxines, less aflatoxines, geosmin level, phenolic aromas, lacchase,polyphenol oxidases and peroxidases, nitrate content etc.

Sustainable agriculture, comprising nutrient use efficiency, especiallynitrogen (N)-use efficiency, phosphours (P)-use efficiency, water useefficiency, improved transpiration, respiration and/or CO₂ assimilationrate, better nodulation, improved Ca-metabolism etc.

Delayed senescence, comprising improvement of plant physiology which ismanifested, for example, in a longer grain filling phase, leading tohigher yield, a longer duration of green leaf colouration of the plantand thus comprising colour (greening), water content, dryness etc.Accordingly, in the context of the present invention, it has been foundthat the specific inventive application of the active compoundcombination makes it possible to prolong the green leaf area duration,which delays the maturation (senescence) of the plant. The mainadvantage to the farmer is a longer grain filling phase leading tohigher yield. There is also an advantage to the farmer on the basis ofgreater flexibility in the harvesting time.

Therein “sedimentation value” is a measure for protein quality anddescribes according to Zeleny (Zeleny value) the degree of sedimentationof flour suspended in a lactic acid solution during a standard timeinterval. This is taken as a measure of the baking quality. Swelling ofthe gluten fraction of flour in lactic acid solution affects the rate ofsedimentation of a flour suspension. Both a higher gluten content and abetter gluten quality give rise to slower sedimentation and higherZeleny test values. The sedimentation value of flour depends on thewheat protein composition and is mostly correlated to the proteincontent, the wheat hardness, and the volume of pan and hearth loaves. Astronger correlation between loaf volume and Zeleny sedimentation volumecompared to SDS sedimentation volume could be due to the protein contentinfluencing both the volume and Zeleny value (Czech. J. Food Sci. Vol.21, No. 3: 91-96, 2000).

Further the “falling number” as mentioned herein is a measure for thebaking quality of cereals, especially of wheat. The falling number testindicates that sprout damage may have occurred. It means that changes tothe physical properties of the starch portion of the wheat kernel hasalready happened. Therein, the falling number instrument analyzesviscosity by measuring the resistance of a flour and water paste to afalling plunger. The time (in seconds) for this to happen is known asthe falling number. The falling number results are recorded as an indexof enzyme activity in a wheat or flour sample and results are expressedin time as seconds. A high falling number (for example, above 300seconds) indicates minimal enzyme activity and sound quality wheat orflour. A low falling number (for example, below 250 seconds) indicatessubstantial enzyme activity and sprout-damaged wheat or flour.

The term “more developed root system”/“improved root growth” refers tolonger root system, deeper root growth, faster root growth, higher rootdry/fresh weight, higher root volume, larger root surface area, biggerroot diameter, higher root stability, more root branching, higher numberof root hairs, and/or more root tips and can be measured by analyzingthe root architecture with suitable methodologies and Image analysisprogrammes (e.g. WinRhizo).

The term “crop water use efficiency” refers technically to the mass ofagriculture produce per unit water consumed and economically to thevalue of product(s) produced per unit water volume consumed and can e.g.be measured in terms of yield per ha, biomass of the plants,thousand-kernel mass, and the number of ears per m².

The term “nitrogen-use efficiency” refers technically to the mass ofagriculture produce per unit nitrogen consumed and economically to thevalue of product(s) produced per unit nitrogen consumed, reflectinguptake and utilization efficiency.

Improvement in greening/improved colour and improved photosyntheticefficiency as well as the delay of senescence can be measured withwell-known techniques such as a HandyPea system (Hansatech). Fv/Fm is aparameter widely used to indicate the maximum quantum efficiency ofphotosystem II (PSII). This parameter is widely considered to be aselective indication of plant photosynthetic performance with healthysamples typically achieving a maximum Fv/Fm value of approx. 0.85.Values lower than this will be observed if a sample has been exposed tosome type of biotic or abiotic stress factor which has reduced thecapacity for photochemical quenching of energy within PSII. Fv/Fm ispresented as a ratio of variable fluorescence (Fv) over the maximumfluorescence value (Fm). The Performance Index is essentially anindicator of sample vitality. (See e.g. Advanced Techniques in SoilMicrobiology, 2007, 11, 319-341; Applied Soil Ecology, 2000, 15,169-182.)

The improvement in greening/improved colour and improved photosyntheticefficiency as well as the delay of senescence can also be assessed bymeasurement of the net photosynthetic rate (Pn), measurement of thechlorophyll content, e.g. by the pigment extraction method of Zieglerand Ehle, measurement of the photochemical efficiency (Fv/Fm ratio),determination of shoot growth and final root and/or canopy biomass,determination of tiller density as well as of root mortality.

Within the context of the present invention preference is given toimproving plant physiology effects which are selected from the groupcomprising: enhanced root growth/more developed root system, improvedgreening, improved water use efficiency (correlating to reduced waterconsumption), improved nutrient use efficiency, comprising especiallyimproved nitrogen (N)-use efficiency, delayed senescence and enhancedyield.

Within the enhancement of yield preference is given as to an improvementin the sedimentation value and the falling number as well as to theimprovement of the protein and sugar content—especially with plantsselected from the group of cereals (preferably wheat).

Preferably the novel use of the fungicidal compositions of the presentinvention relates to a combined use of a) preventively and/or curativelycontrolling pathogenic fungi and/or nematodes, with or withoutresistance management, and b) at least one of enhanced root growth,improved greening, improved water use efficiency, delayed senescence andenhanced yield. From group b) enhancement of root system, water useefficiency and N-use efficiency is particularly preferred.

Seed Treatment

The invention further comprises a method for treating seed.

The invention further relates to seed which has been treated by one ofthe methods described in the previous paragraph. The inventive seeds areemployed in methods for the protection of seed from harmfulmicroorganisms. In these methods, seed treated with at least oneinventive active ingredient is used.

The inventive active ingredients or compositions are also suitable fortreating seed. A large part of the damage to crop plants caused byharmful organisms is triggered by the infection of the seed duringstorage or after sowing, and also during and after germination of theplant. This phase is particularly critical since the roots and shoots ofthe growing plant are particularly sensitive, and even minor damage mayresult in the death of the plant. There is therefore a great interest inprotecting the seed and the germinating plant by using appropriatecompositions.

The control of phytopathogenic fungi by treating the seed of plants hasbeen known for a long time and is the subject of constant improvements.However, the treatment of seed entails a series of problems which cannotalways be solved in a satisfactory manner. For instance, it is desirableto develop methods for protecting the seed and the germinating plant,which dispense with, or at least significantly reduce, the additionaldeployment of crop protection compositions after planting or afteremergence of the plants. It is also desirable to optimize the amount ofthe active ingredient used so as to provide the best possible protectionfor the seed and the germinating plant from attack by phytopathogenicfungi, but without damaging the plant itself by the active ingredientemployed. In particular, methods for the treatment of seed should alsotake account of the intrinsic fungicidal properties of transgenic plantsin order to achieve optimal protection of the seed and the germinatingplant with a minimum expenditure of crop protection compositions.

The present invention therefore also relates to a method for protectionof seed and germinating plants from attack by phytopathogenic fungi, bytreating the seed with an inventive composition. The invention likewiserelates to the use of the inventive compositions for treatment of seedto protect the seed and the germinating plant from phytopathogenicfungi. The invention further relates to seed which has been treated withan inventive composition for protection from phytopathogenic fungi.

The control of phytopathogenic fungi which damage plants post-emergenceis effected primarily by treating the soil and the above-ground parts ofplants with crop protection compositions. Owing to the concernsregarding a possible influence of the crop protection compositions onthe environment and the health of humans and animals, there are effortsto reduce the amount of active ingredients deployed.

One of the advantages of the present invention is that the particularsystemic properties of the inventive active ingredients and compositionsmean that treatment of the seed with these active ingredients andcompositions not only protects the seed itself, but also the resultingplants after emergence, from phytopathogenic fungi. In this way, theimmediate treatment of the crop at the time of sowing or shortlythereafter can be dispensed with.

It is likewise considered to be advantageous that the inventive activeingredients or compositions can especially also be used with transgenicseed, in which case the plant growing from this seed is capable ofexpressing a protein which acts against pests. By virtue of thetreatment of such seed with the inventive active ingredients orcompositions, merely the expression of the protein, for example aninsecticidal protein, can control certain pests. Surprisingly, a furthersynergistic effect can be observed in this case, which additionallyincreases the effectiveness for protection against attack by pests.

The inventive compositions are suitable for protecting seed of any plantvariety which is used in agriculture, in greenhouses, in forests or inhorticulture and viticulture. In particular, this is the seed of cereals(such as wheat, barley, rye, triticale, sorghum/millet and oats), maize,cotton, soya beans, rice, potatoes, sunflower, bean, coffee, beet (forexample sugar beet and fodder beet), peanut, oilseed rape, poppy, olive,coconut, cocoa, sugar cane, tobacco, vegetables (such as tomato,cucumbers, onions and lettuce), turf and ornamentals (see also below).The treatment of the seed of cereals (such as wheat, barley, rye,triticale and oats), maize and rice is of particular significance.

As also described below, the treatment of transgenic seed with theinventive active ingredients or compositions is of particularsignificance. This relates to the seed of plants containing at least oneheterologous gene. Definition and examples of suitable heterologousgenes are given below.

In the context of the present invention, the inventive composition isapplied to the seed alone or in a suitable formulation. Preferably, theseed is treated in a state in which it is sufficiently stable for nodamage to occur in the course of treatment. In general, the seed can betreated at any time between harvest and sowing. It is customary to useseed which has been separated from the plant and freed from cobs,shells, stalks, coats, hairs or the flesh of the fruits. For example, itis possible to use seed which has been harvested, cleaned and dried downto a moisture content of less than 15% by weight. Alternatively, it isalso possible to use seed which, after drying, for example, has beentreated with water and then dried again.

When treating the seed, care must generally be taken that the amount ofthe inventive composition applied to the seed and/or the amount offurther additives is selected such that the germination of the seed isnot impaired, or that the resulting plant is not damaged. This has to beborne in mind in particular in the case of active ingredients which canhave phytotoxic effects at certain application rates.

The inventive compositions can be applied directly, i.e. withoutcontaining any other components and without having been diluted. Ingeneral, it is preferable to apply the compositions to the seed in theform of a suitable formulation. Suitable formulations and methods forseed treatment are known to those skilled in the art and are described,for example, in the following documents: U.S. Pat. No. 4,272,417, U.S.Pat. No. 4,245,432, U.S. Pat. No. 4,808,430, U.S. Pat. No. 5,876,739, US2003/0176428 A1, WO 2002/080675, WO 2002/028186.

The active ingredients usable in accordance with the invention can beconverted to the customary seed dressing formulations, such assolutions, emulsions, suspensions, powders, foams, slurries or othercoating compositions for seed, and also ULV formulations.

These formulations are prepared in a known manner, by mixing the activeingredients with customary additives, for example customary extendersand also solvents or diluents, dyes, wetting agents, dispersants,emulsifiers, antifoams, preservatives, secondary thickeners, adhesives,gibberellins and also water.

Useful dyes which may be present in the seed dressing formulationsusable in accordance with the invention are all dyes which are customaryfor such purposes. It is possible to use either pigments, which aresparingly soluble in water, or dyes, which are soluble in water.Examples include the dyes known by the names Rhodamine B, C.I. PigmentRed 112 and C.I. Solvent Red 1.

Useful wetting agents which may be present in the seed dressingformulations usable in accordance with the invention are all substanceswhich promote wetting and which are conventionally used for theformulation of active agrochemical ingredients. Preference is given tousing alkyl naphthalenesulphonates, such as diisopropyl or diisobutylnaphthalenesulphonates.

Useful dispersants and/or emulsifiers which may be present in the seeddressing formulations usable in accordance with the invention are allnonionic, anionic and cationic dispersants conventionally used for theformulation of active agrochemical ingredients. Usable with preferenceare nonionic or anionic dispersants or mixtures of nonionic or anionicdispersants. Suitable nonionic dispersants include especially ethyleneoxide/propylene oxide block polymers, alkylphenol polyglycol ethers andtristryrylphenol polyglycol ether, and the phosphated or sulphatedderivatives thereof. Suitable anionic dispersants are especiallylignosulphonates, polyacrylic acid salts and arylsulphonate/formaldehydecondensates.

Antifoams which may be present in the seed dressing formulations usablein accordance with the invention are all foam-inhibiting substancesconventionally used for the formulation of active agrochemicalingredients. Silicone antifoams and magnesium stearate can be used withpreference.

Preservatives which may be present in the seed dressing formulationsusable in accordance with the invention are all substances usable forsuch purposes in agrochemical compositions. Examples includedichlorophene and benzyl alcohol hemiformal.

Secondary thickeners which may be present in the seed dressingformulations usable in accordance with the invention are all substancesusable for such purposes in agrochemical compositions. Preferredexamples include cellulose derivatives, acrylic acid derivatives,xanthan, modified clays and finely divided silica.

Adhesives which may be present in the seed dressing formulations usablein accordance with the invention are all customary binders usable inseed dressing products. Preferred examples include polyvinylpyrrolidone,polyvinyl acetate, polyvinyl alcohol and tylose.

The gibberellins which may be present in the seed dressing formulationsusable in accordance with the invention may preferably be gibberellinsA1, A3 (=gibberellic acid), A4 and A7; particular preference is given tousing gibberellic acid. The gibberellins are known (cf. R. Wegler“Chemie der Pflanzenschutz-und Schädlingsbekämpfungsmittel” [Chemistryof the Crop Protection Compositions and Pesticides], vol. 2, SpringerVerlag, 1970, p. 401-412).

The seed dressing formulations usable in accordance with the inventioncan be used, either directly or after previously having been dilutedwith water, for the treatment of a wide range of different seed,including the seed of transgenic plants. In this case, additionalsynergistic effects may also occur in interaction with the substancesformed by expression.

For treatment of seed with the seed dressing formulations usable inaccordance with the invention, or the preparations prepared therefrom byadding water, all mixing units usable customarily for the seed dressingare useful. Specifically, the procedure in the seed dressing is to placethe seed into a mixer, to add the particular desired amount of seeddressing formulations, either as such or after prior dilution withwater, and to mix everything until the formulation is distributedhomogeneously on the seed. If appropriate, this is followed by a dryingprocess.

Mycotoxins

In addition, the inventive treatment can reduce the mycotoxin content inthe harvested material and the foods and feeds prepared therefrom.Mycotoxins include particularly, but not exclusively, the following:deoxynivalenol (DON), nivalenol, 15-Ac-DON, 3-Ac-DON, T2- and HT2-toxin,fumonisins, zearalenon, moniliformin, fusarin, diaceotoxyscirpenol(DAS), beauvericin, enniatin, fusaroproliferin, fusarenol, ochratoxins,patulin, ergot alkaloids and aflatoxins which can be produced, forexample, by the following fungi: Fusarium spec., such as F. acuminatum,F. asiaticum, F. avenaceum, F. crookwellense, F. culmorum, F.graminearum (Gibberella zeae), F. equiseti, F. fujikoroi, F. musarum, F.oxysporum, F. proliferatum, F. poae, F. pseudograminearum, F.sambucinum, F. scirpi, F. semitectum, F. solani, F. sporotrichoides, F.langsethiae, F. subglutinans, F. tricinctum, F. verticillioides etc.,and also by Aspergillus spec., such as A. flavus, A. parasiticus, A.nomius, A. ochraceus, A. clavatus, A. terreus, A. versicolor,Penicillium spec., such as P. verrucosum, P. viridicatum, P. citrinum,P. expansum, P. claviforme, P. roqueforti, Claviceps spec., such as C.purpurea, C. fusiformis, C. paspali, C. africana, Stachybotrys spec. andothers.

Material Protection

The inventive active ingredients or compositions can also be used in theprotection of materials, for protection of industrial materials againstattack and destruction by harmful microorganisms, for example fungi andinsects.

In addition, the inventive compounds can be used as antifoulingcompositions, alone or in combinations with other active ingredients.

Industrial materials in the present context are understood to meaninanimate materials which have been prepared for use in industry. Forexample, industrial materials which are to be protected by inventiveactive ingredients from microbial alteration or destruction may beadhesives, glues, paper, wallpaper and board/cardboard, textiles,carpets, leather, wood, fibers and tissues, paints and plastic articles,cooling lubricants and other materials which can be infected with ordestroyed by microorganisms. Parts of production plants and buildings,for example cooling-water circuits, cooling and heating systems andventilation and air-conditioning units, which may be impaired by theproliferation of microorganisms may also be mentioned within the scopeof the materials to be protected. Industrial materials within the scopeof the present invention preferably include adhesives, sizes, paper andcard, leather, wood, paints, cooling lubricants and heat transferfluids, more preferably wood.

The inventive active ingredients or compositions may prevent adverseeffects, such as rotting, decay, discoloration, decoloration orformation of mould.

In the case of treatment of wood the compounds/compositions according tothe invention may also be used against fungal diseases liable to grow onor inside timber. The term “timber” means all types of species of wood,and all types of working of this wood intended for construction, forexample solid wood, high-density wood, laminated wood, and plywood. Themethod for treating timber according to the invention mainly consists incontacting one or more compounds according to the invention or acomposition according to the invention; this includes for example directapplication, spraying, dipping, injection or any other suitable means.

In addition, the inventive compounds can be used to protect objectswhich come into contact with saltwater or brackish water, especiallyhulls, screens, nets, buildings, moorings and signalling systems, fromfouling.

The inventive method for controlling unwanted fungi can also be employedfor protecting storage goods. Storage goods are understood to meannatural substances of vegetable or animal origin or processed productsthereof which are of natural origin, and for which long-term protectionis desired. Storage goods of vegetable origin, for example plants orplant parts, such as stems, leaves, tubers, seeds, fruits, grains, canbe protected freshly harvested or after processing by (pre)drying,moistening, comminuting, grinding, pressing or roasting. Storage goodsalso include timber, both unprocessed, such as construction timber,electricity poles and barriers, or in the form of finished products,such as furniture. Storage goods of animal origin are, for example,hides, leather, furs and hairs. The inventive active ingredients mayprevent adverse effects, such as rotting, decay, discoloration,decoloration or formation of mould.

Microorganisms capable of degrading or altering the industrial materialsinclude, for example, bacteria, fungi, yeasts, algae and slimeorganisms. The inventive active ingredients preferably act againstfungi, especially moulds, wood-discoloring and wood-destroying fungi(Ascomycetes, Basidiomycetes, Deuteromycetes and Zygomycetes), andagainst slime organisms and algae. Examples include microorganisms ofthe following genera: Alternaria, such as Alternaria tenuis;Aspergillus, such as Aspergillus niger; Chaetomium, such as Chaetomiumglobosum; Coniophora, such as Coniophora puetana; Lentinus, such asLentinus tigrinus; Penicillium, such as Penicillium glaucum; Polyporus,such as Polyporus versicolor; Aureobasidium, such as Aureobasidiumpullulans; Sclerophoma, such as Sclerophoma pityophila; Trichoderma,such as Trichoderma viride; Ophiostoma spp., Ceratocystis spp., Humicolaspp., Petriella spp., Trichurus spp., Coriolus spp., Gloeophyllum spp.,Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp.,Cladosporium spp., Paecilomyces spp. Mucor spp., Escherichia, such asEscherichia coli; Pseudomonas, such as Pseudomonas aeruginosa;Staphylococcus, such as Staphylococcus aureus, Candida spp. andSaccharomyces spp., such as Saccharomyces cerevisae.

Antimycotic Activity

In addition, the inventive active ingredients also have very goodantimycotic activity. They have a very broad antimycotic activityspectrum, especially against dermatophytes and yeasts, moulds anddiphasic fungi (for example against Candida species, such as C.albicans, C. glabrata), and Epidermophyton floccosum, Aspergillusspecies, such as A. niger and A. fumigatus, Trichophyton species, suchas T. mentagrophytes, Microsporon species such as M. canis and M.audouinii. The list of these fungi by no means constitutes a restrictionof the mycotic spectrum covered, and is merely of illustrativecharacter.

The inventive active ingredients can therefore be used both in medicaland in non-medical applications.

GMO

As already mentioned above, it is possible to treat all plants and theirparts in accordance with the invention. In a preferred embodiment, wildplant species and plant cultivars, or those obtained by conventionalbiological breeding methods, such as crossing or protoplast fusion, andalso parts thereof, are treated. In a further preferred embodiment,transgenic plants and plant cultivars obtained by genetic engineeringmethods, if appropriate in combination with conventional methods(Genetically Modified Organisms), and parts thereof are treated. Theterms “parts” or “parts of plants” or “plant parts” have been explainedabove. More preferably, plants of the plant cultivars which arecommercially available or are in use are treated in accordance with theinvention. Plant cultivars are understood to mean plants which have newproperties (“traits”) and have been obtained by conventional breeding,by mutagenesis or by recombinant DNA techniques. They can be cultivars,varieties, bio- or genotypes.

The method of treatment according to the invention can be used in thetreatment of genetically modified organisms (GMOs), e.g. plants orseeds. Genetically modified plants (or transgenic plants) are plants ofwhich a heterologous gene has been stably integrated into genome. Theexpression “heterologous gene” essentially means a gene which isprovided or assembled outside the plant and when introduced in thenuclear, chloroplastic or mitochondrial genome gives the transformedplant new or improved agronomic or other properties by expressing aprotein or polypeptide of interest or by downregulating or silencingother gene(s) which are present in the plant (using for example,antisense technology, cosuppression technology, RNAinterference—RNAi—technology or microRNA—miRNA—technology). Aheterologous gene that is located in the genome is also called atransgene. A transgene that is defined by its particular location in theplant genome is called a transformation or transgenic event.

Depending on the plant species or plant cultivars, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, reduced application ratesand/or a widening of the activity spectrum and/or an increase in theactivity of the active compounds and compositions which can be usedaccording to the invention, better plant growth, increased tolerance tohigh or low temperatures, increased tolerance to drought or to water orsoil salt content, increased flowering performance, easier harvesting,accelerated maturation, higher harvest yields, bigger fruits, largerplant height, greener leaf color, earlier flowering, higher qualityand/or a higher nutritional value of the harvested products, highersugar concentration within the fruits, better storage stability and/orprocessability of the harvested products are possible, which exceed theeffects which were actually to be expected.

Plants and plant cultivars which are preferably to be treated accordingto the invention include all plants which have genetic material whichimpart particularly advantageous, useful traits to these plants (whetherobtained by breeding and/or biotechnological means).

Plants and plant cultivars which are also preferably to be treatedaccording to the invention are resistant against one or more bioticstresses, i.e. said plants show a better defense against animal andmicrobial pests, such as against nematodes, insects, mites,phytopathogenic fungi, bacteria, viruses and/or viroids.

Examples of nematode or insect resistant plants are described in e.g.U.S. patent application Ser. Nos. 11/765,491, 11/765,494, 10/926,819,10/782,020, 12/032,479, 10/783,417, 10/782,096, 11/657,964, 12/192,904,11/396,808, 12/166,253, 12/166,239, 12/166,124, 12/166,209, 11/762,886,12/364,335, 11/763,947, 12/252,453, 12/209,354, 12/491,396, 12/497,221,12/644,632, 12/646,004, 12/701,058, 12/718,059, 12/721,595, 12/638,591.

Plants and plant cultivars which may also be treated according to theinvention are those plants which are resistant to one or more abioticstresses. Abiotic stress conditions may include, for example, drought,cold temperature exposure, heat exposure, osmotic stress, flooding,increased soil salinity, increased mineral exposure, ozone exposure,high light exposure, limited availability of nitrogen nutrients, limitedavailability of phosphorus nutrients, shade avoidance.

Plants and plant cultivars which may also be treated according to theinvention, are those plants characterized by enhanced yieldcharacteristics. Increased yield in said plants can be the result of,for example, improved plant physiology, growth and development, such aswater use efficiency, water retention efficiency, improved nitrogen use,enhanced carbon assimilation, improved photosynthesis, increasedgermination efficiency and accelerated maturation. Yield can furthermorebe affected by improved plant architecture (under stress and non-stressconditions), including but not limited to, early flowering, floweringcontrol for hybrid seed production, seedling vigor, plant size,internode number and distance, root growth, seed size, fruit size, podsize, pod or ear number, seed number per pod or ear, seed mass, enhancedseed filling, reduced seed dispersal, reduced pod dehiscence and lodgingresistance. Further yield traits include seed composition, such ascarbohydrate content, protein content, oil content and composition,nutritional value, reduction in anti-nutritional compounds, improvedprocessability and better storage stability.

Plants that may be treated according to the invention are hybrid plantsthat already express the characteristic of heterosis or hybrid vigorwhich results in generally higher yield, vigor, health and resistancetowards biotic and abiotic stresses). Such plants are typically made bycrossing an inbred male-sterile parent line (the female parent) withanother inbred male-fertile parent line (the male parent). Hybrid seedis typically harvested from the male sterile plants and sold to growers.Male sterile plants can sometimes (e.g. in corn) be produced bydetasseling, i.e. the mechanical removal of the male reproductive organs(or males flowers) but, more typically, male sterility is the result ofgenetic determinants in the plant genome. In that case, and especiallywhen seed is the desired product to be harvested from the hybrid plantsit is typically useful to ensure that male fertility in the hybridplants is fully restored. This can be accomplished by ensuring that themale parents have appropriate fertility restorer genes which are capableof restoring the male fertility in hybrid plants that contain thegenetic determinants responsible for male-sterility. Geneticdeterminants for male sterility may be located in the cytoplasm.Examples of cytoplasmic male sterility (CMS) were for instance describedin Brassica species (WO 92/05251, WO 95/09910, WO 98/27806, WO05/002324, WO 06/021972 and U.S. Pat. No. 6,229,072). However, geneticdeterminants for male sterility can also be located in the nucleargenome. Male sterile plants can also be obtained by plant biotechnologymethods such as genetic engineering. A particularly useful means ofobtaining male-sterile plants is described in WO 89/10396 in which, forexample, a ribonuclease such as barnase is selectively expressed in thetapetum cells in the stamens. Fertility can then be restored byexpression in the tapetum cells of a ribonuclease inhibitor such asbarstar (e.g. WO 91/02069).

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may be treated according to the inventionare herbicide-tolerant plants, i.e. plants made tolerant to one or moregiven herbicides. Such plants can be obtained either by genetictransformation, or by selection of plants containing a mutationimparting such herbicide tolerance.

Herbicide-resistant plants are for example glyphosate-tolerant plants,i.e. plants made tolerant to the herbicide glyphosate or salts thereof.Plants can be made tolerant to glyphosate through different means. Forexample, glyphosate-tolerant plants can be obtained by transforming theplant with a gene encoding the enzyme 5-enolpyruvylshikimate-3-phosphatesynthase (EPSPS). Examples of such EPSPS genes are the AroA gene (mutantCT7) of the bacterium Salmonella typhimurium (Science 1983, 221,370-371), the CP4 gene of the bacterium Agrobacterium sp. (Curr. TopicsPlant Physiol. 1992, 7, 139-145), the genes encoding a Petunia EPSPS(Science 1986, 233, 478-481), a Tomato EPSPS (J. Biol. Chem. 1988, 263,4280-4289), or an Eleusine EPSPS (WO 01/66704). It can also be a mutatedEPSPS as described in for example EP 0837944, WO 00/66746, WO 00/66747or WO 02/26995. Glyphosate-tolerant plants can also be obtained byexpressing a gene that encodes a glyphosate oxido-reductase enzyme asdescribed in U.S. Pat. No. 5,776,760 and U.S. Pat. No. 5,463,175.Glyphosate-tolerant plants can also be obtained by expressing a genethat encodes a glyphosate acetyl transferase enzyme as described in forexample WO 02/036782, WO 03/092360, WO 2005/012515 and WO 2007/024782.Glyphosate-tolerant plants can also be obtained by selecting plantscontaining naturally-occurring mutations of the above-mentioned genes,as described in for example WO 01/024615 or WO 03/013226. Plantsexpressing EPSPS genes that confer glyphosate tolerance are described ine.g. U.S. patent application Ser. Nos. 11/517,991, 10/739,610,12/139,408, 12/352,532, 11/312,866, 11/315,678, 12/421,292, 11/400,598,11/651,752, 11/681,285, 11/605,824, 12/468,205, 11/760,570, 11/762,526,11/769,327, 11/769,255, 11/943,801 or 12/362,774. Plants comprisingother genes that confer glyphosate tolerance, such as decarboxylasegenes, are described in e.g. U.S. patent application Ser. Nos.11/588,811, 11/185,342, 12/364,724, 11/185,560 or 12/423,926.

Other herbicide resistant plants are for example plants that are madetolerant to herbicides inhibiting the enzyme glutamine synthase, such asbialaphos, phosphinothricin or glufosinate. Such plants can be obtainedby expressing an enzyme detoxifying the herbicide or a mutant glutaminesynthase enzyme that is resistant to inhibition, e.g. described in U.S.patent application Ser. No. 11/760,602. One such efficient detoxifyingenzyme is an enzyme encoding a phosphinothricin acetyltransferase (suchas the bar or pat protein from Streptomyces species). Plants expressingan exogenous phosphinothricin acetyltransferase are for exampledescribed in U.S. Pat. Nos. 5,561,236; 5,648,477; 5,646,024; 5,273,894;5,637,489; 5,276,268; 5,739,082; 5,908,810 and 7,112,665.

Further herbicide-tolerant plants are also plants that are made tolerantto the herbicides inhibiting the enzyme hydroxyphenylpyruvatedioxygenase(HPPD). HPPD is an enzyme that catalyze the reaction in whichpara-hydroxyphenylpyruvate (HPP) is transformed into homogentisate.Plants tolerant to HPPD-inhibitors can be transformed with a geneencoding a naturally-occurring resistant HPPD enzyme, or a gene encodinga mutated or chimeric HPPD enzyme as described in WO 96/38567, WO99/24585, WO 99/24586, WO 09/144079, WO 02/046387, or U.S. Pat. No.6,768,044. Tolerance to HPPD-inhibitors can also be obtained bytransforming plants with genes encoding certain enzymes enabling theformation of homogentisate despite the inhibition of the native HPPDenzyme by the HPPD-inhibitor. Such plants and genes are described in WO99/34008 and WO 02/36787. Tolerance of plants to HPPD inhibitors canalso be improved by transforming plants with a gene encoding an enzymehaving prephenate deshydrogenase (PDH) activity in addition to a geneencoding an HPPD-tolerant enzyme, as described in WO 04/024928. Further,plants can be made more tolerant to HPPD-inhibitor herbicides by addinginto their genome a gene encoding an enzyme capable of metabolizing ordegrading HPPD inhibitors, such as the CYP450 enzymes shown in WO2007/103567 and WO 2008/150473.

Still further herbicide resistant plants are plants that are madetolerant to acetolactate synthase (ALS) inhibitors. Known ALS-inhibitorsinclude, for example, sulfonylurea, imidazolinone, triazolopyrimidines,pryimidinyoxy(thio)benzoates, and/or sulfonylaminocarbonyltriazolinoneherbicides. Different mutations in the ALS enzyme (also known asacetohydroxyacid synthase, AHAS) are known to confer tolerance todifferent herbicides and groups of herbicides, as described for examplein Tranel and Wright (Weed Science 2002, 50, 700-712), but also, in U.S.Pat. Nos. 5,605,011, 5,378,824, 5,141,870, and 5,013,659. The productionof sulfonylurea-tolerant plants and imidazolinone-tolerant plants isdescribed in U.S. Pat. Nos. 5,605,011; 5,013,659; 5,141,870; 5,767,361;5,731,180; 5,304,732; 4,761,373; 5,331,107; 5,928,937; and 5,378,824;and WO 96/33270. Other imidazolinone-tolerant plants are also describedin for example WO 2004/040012, WO 2004/106529, WO 2005/020673, WO2005/093093, WO 2006/007373, WO 2006/015376, WO 2006/024351, and WO2006/060634. Further sulfonylurea- and imidazolinone-tolerant plants arealso described in for example WO 2007/024782 and U.S. Patent Application61/288,958.

Other plants tolerant to imidazolinone and/or sulfonylurea can beobtained by induced mutagenesis, selection in cell cultures in thepresence of the herbicide or mutation breeding as described for examplefor soybeans in U.S. Pat. No. 5,084,082, for rice in WO 97/41218, forsugar beet in U.S. Pat. No. 5,773,702 and WO 99/057965, for lettuce inU.S. Pat. No. 5,198,599, or for sunflower in WO 01/065922.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are insect-resistant transgenic plants, i.e. plants maderesistant to attack by certain target insects. Such plants can beobtained by genetic transformation, or by selection of plants containinga mutation imparting such insect resistance.

An “insect-resistant transgenic plant”, as used herein, includes anyplant containing at least one transgene comprising a coding sequenceencoding:

-   1) an insecticidal crystal protein from Bacillus thuringiensis or an    insecticidal portion thereof, such as the insecticidal crystal    proteins listed by Crickmore et al. (1998, Microbiology and    Molecular Biology Reviews, 62: 807-813), updated by Crickmore et    al. (2005) at the Bacillus thuringiensis toxin nomenclature, online    at: http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/), or    insecticidal portions thereof, e.g., proteins of the Cry protein    classes Cry1Ab, Cry1Ac, Cry1B, Cry1C, Cry1D, Cry1F, Cry2Ab, Cry3Aa,    or Cry3Bb or insecticidal portions thereof (e.g. EP-A 1 999 141 and    WO 2007/107302), or such proteins encoded by synthetic genes as e.g.    described in and U.S. patent application Ser. No. 12/249,016; or-   2) a crystal protein from Bacillus thuringiensis or a portion    thereof which is insecticidal in the presence of a second other    crystal protein from Bacillus thuringiensis or a portion thereof,    such as the binary toxin made up of the Cry34 and Cry35 crystal    proteins (Nat. Biotechnol. 2001, 19, 668-72; Applied Environm.    Microbiol. 2006, 71, 1765-1774) or the binary toxin made up of the    Cry1A or Cry1F proteins and the Cry2Aa or Cry2Ab or Cry2Ae proteins    (U.S. patent application Ser. No. 12/214,022 and EP-A 2 300 618); or-   3) a hybrid insecticidal protein comprising parts of different    insecticidal crystal proteins from Bacillus thuringiensis, such as a    hybrid of the proteins of 1) above or a hybrid of the proteins of 2)    above, e.g., the Cry1A.105 protein produced by corn event MON89034    (WO 2007/027777); or-   4) a protein of any one of 1) to 3) above wherein some, particularly    1 to 10, amino acids have been replaced by another amino acid to    obtain a higher insecticidal activity to a target insect species,    and/or to expand the range of target insect species affected, and/or    because of changes introduced into the encoding DNA during cloning    or transformation, such as the Cry3Bb1 protein in corn events MON863    or MON88017, or the Cry3A protein in corn event MIR604; or-   5) an insecticidal secreted protein from Bacillus thuringiensis or    Bacillus cereus, or an insecticidal portion thereof, such as the    vegetative insecticidal (VIP) proteins listed at:    http://www.lifesci.sussex.ac.uk/home/Neil_Crickmore/Bt/vip.html,    e.g., proteins from the VIP3Aa protein class; or-   6) a secreted protein from Bacillus thuringiensis or Bacillus cereus    which is insecticidal in the presence of a second secreted protein    from Bacillus thuringiensis or B. cereus, such as the binary toxin    made up of the VIP1A and VIP2A proteins (WO 94/21795); or-   7) a hybrid insecticidal protein comprising parts from different    secreted proteins from Bacillus thuringiensis or Bacillus cereus,    such as a hybrid of the proteins in 1) above or a hybrid of the    proteins in 2) above; or-   8) a protein of any one of 5) to 7) above wherein some, particularly    1 to 10, amino acids have been replaced by another amino acid to    obtain a higher insecticidal activity to a target insect species,    and/or to expand the range of target insect species affected, and/or    because of changes introduced into the encoding DNA during cloning    or transformation (while still encoding an insecticidal protein),    such as the VIP3Aa protein in cotton event COT102; or-   9) a secreted protein from Bacillus thuringiensis or Bacillus cereus    which is insecticidal in the presence of a crystal protein from    Bacillus thuringiensis, such as the binary toxin made up of VIP3 and    Cry1A or Cry1F (U.S. Patent Applications 61/126,083 and 61/195,019),    or the binary toxin made up of the VIP3 protein and the Cry2Aa or    Cry2Ab or Cry2Ae proteins (U.S. patent application Ser. No.    12/214,022 and EP-A 2 300 618).-   10) a protein of 9) above wherein some, particularly 1 to 10, amino    acids have been replaced by another amino acid to obtain a higher    insecticidal activity to a target insect species, and/or to expand    the range of target insect species affected, and/or because of    changes introduced into the encoding DNA during cloning or    transformation (while still encoding an insecticidal protein)

Of course, an insect-resistant transgenic plant, as used herein, alsoincludes any plant comprising a combination of genes encoding theproteins of any one of the above classes 1 to 10. In one embodiment, aninsect-resistant plant contains more than one transgene encoding aprotein of any one of the above classes 1 to 10, to expand the range oftarget insect species affected when using different proteins directed atdifferent target insect species, or to delay insect resistancedevelopment to the plants by using different proteins insecticidal tothe same target insect species but having a different mode of action,such as binding to different receptor binding sites in the insect.

An “insect-resistant transgenic plant”, as used herein, further includesany plant containing at least one transgene comprising a sequenceproducing upon expression a double-stranded RNA which upon ingestion bya plant insect pest inhibits the growth of this insect pest, asdescribed e.g. in WO 2007/080126, WO 2006/129204, WO 2007/074405, WO2007/080127 and WO 2007/035650.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are tolerant to abiotic stresses. Such plants can be obtainedby genetic transformation, or by selection of plants containing amutation imparting such stress resistance. Particularly useful stresstolerance plants include:

-   1) plants which contain a transgene capable of reducing the    expression and/or the activity of poly(ADP-ribose) polymerase (PARP)    gene in the plant cells or plants as described in WO 00/04173, WO    2006/045633, EP-A 1 807 519, or EP-A 2 018 431.-   2) plants which contain a stress tolerance enhancing transgene    capable of reducing the expression and/or the activity of the PARG    encoding genes of the plants or plants cells, as described e.g. in    WO 2004/090140.-   3) plants which contain a stress tolerance enhancing transgene    coding for a plant-functional enzyme of the nicotineamide adenine    dinucleotide salvage synthesis pathway including nicotinamidase,    nicotinate phosphoribosyltransferase, nicotinic acid mononucleotide    adenyl transferase, nicotinamide adenine dinucleotide synthetase or    nicotine amide phosphorybosyltransferase as described e.g. in EP-A 1    794 306, WO 2006/133827, WO 2007/107326, EP-A 1 999 263, or WO    2007/107326.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention show altered quantity, quality and/or storage-stability of theharvested product and/or altered properties of specific ingredients ofthe harvested product such as:

-   1) transgenic plants which synthesize a modified starch, which in    its physical-chemical characteristics, in particular the amylose    content or the amylose/amylopectin ratio, the degree of branching,    the average chain length, the side chain distribution, the viscosity    behaviour, the gelling strength, the starch grain size and/or the    starch grain morphology, is changed in comparison with the    synthesised starch in wild type plant cells or plants, so that this    is better suited for special applications. Said transgenic plants    synthesizing a modified starch are disclosed, for example, in EP-A 0    571 427, WO 95/04826, EP-A 0 719 338, WO 96/15248, WO 96/19581, WO    96/27674, WO 97/11188, WO 97/26362, WO 97/32985, WO 97/42328, WO    97/44472, WO 97/45545, WO 98/27212, WO 98/40503, WO 99/58688, WO    99/58690, WO 99/58654, WO 00/08184, WO 00/08185, WO 00/08175, WO    00/28052, WO 00/77229, WO 01/12782, WO 01/12826, WO 02/101059, WO    03/071860, WO 04/056999, WO 05/030942, WO 2005/030941, WO    2005/095632, WO 2005/095617, WO 2005/095619, WO 2005/095618, WO    2005/123927, WO 2006/018319, WO 2006/103107, WO 2006/108702, WO    2007/009823, WO 00/22140, WO 2006/063862, WO 2006/072603, WO    02/034923, WO 2008/017518, WO 2008/080630, WO 2008/080631, WO    2008/090008, WO 01/14569, WO 02/79410, WO 03/33540, WO 2004/078983,    WO 01/19975, WO 95/26407, WO 96/34968, WO 98/20145, WO 99/12950, WO    99/66050, WO 99/53072, U.S. Pat. No. 6,734,341, WO 00/11192, WO    98/22604, WO 98/32326, WO 01/98509, WO 01/98509, WO 2005/002359,    U.S. Pat. No. 5,824,790, U.S. Pat. No. 6,013,861, WO 94/04693, WO    94/09144, WO 94/11520, WO 95/35026, WO 97/20936, WO 2010/012796, WO    2010/003701,-   2) transgenic plants which synthesize non starch carbohydrate    polymers or which synthesize non starch carbohydrate polymers with    altered properties in comparison to wild type plants without genetic    modification. Examples are plants producing polyfructose, especially    of the inulin and levan-type, as disclosed in EP-A 0 663 956, WO    96/01904, WO 96/21023, WO 98/39460, and WO 99/24593, plants    producing alpha-1,4-glucans as disclosed in WO 95/31553, US    2002031826, U.S. Pat. No. 6,284,479, U.S. Pat. No. 5,712,107, WO    97/47806, WO 97/47807, WO 97/47808 and WO 00/14249, plants producing    alpha-1,6 branched alpha-1,4-glucans, as disclosed in WO 00/73422,    plants producing alternan, as disclosed in e.g. WO 00/47727, WO    00/73422, U.S. Pat. No. 5,908,975 and EP-A 0 728 213,-   3) transgenic plants which produce hyaluronan, as for example    disclosed in WO 2006/032538, WO 2007/039314, WO 2007/039315, WO    2007/039316, JP-A 2006-304779, and WO 2005/012529.-   4) transgenic plants or hybrid plants, such as onions with    characteristics such as ‘high soluble solids content’, ‘low    pungency’ (LP) and/or ‘long storage’ (LS), as described in U.S.    patent application Ser. No. 12/020,360.

Plants or plant cultivars (that can be obtained by plant biotechnologymethods such as genetic engineering) which may also be treated accordingto the invention are plants, such as cotton plants, with altered fibercharacteristics. Such plants can be obtained by genetic transformation,or by selection of plants contain a mutation imparting such alteredfiber characteristics and include:

-   a) Plants, such as cotton plants, containing an altered form of    cellulose synthase genes as described in WO 98/00549.-   b) Plants, such as cotton plants, containing an altered form of rsw2    or rsw3 homologous nucleic acids as described in WO 2004/053219.-   c) Plants, such as cotton plants, with increased expression of    sucrose phosphate synthase as described in WO 01/17333.-   d) Plants, such as cotton plants, with increased expression of    sucrose synthase as described in WO 02/45485.-   e) Plants, such as cotton plants, wherein the timing of the    plasmodesmatal gating at the basis of the fiber cell is altered,    e.g. through downregulation of fiber-selective β-1,3-glucanase as    described in WO 2005/017157, or as described in WO 2009/143995.-   f) Plants, such as cotton plants, having fibers with altered    reactivity, e.g. through the expression of    N-acetylglucosaminetransferase gene including nodC and chitin    synthase genes as described in WO 2006/136351.

Plants or plant cultivars (that can be obtained by plant biotechnologymethods such as genetic engineering) which may also be treated accordingto the invention are plants, such as oilseed rape or related Brassicaplants, with altered oil profile characteristics. Such plants can beobtained by genetic transformation, or by selection of plants contain amutation imparting such altered oil profile characteristics and include:

-   a) Plants, such as oilseed rape plants, producing oil having a high    oleic acid content as described e.g. in U.S. Pat. No. 5,969,169,    U.S. Pat. No. 5,840,946 or U.S. Pat. No. 6,323,392 or U.S. Pat. No.    6,063,947-   b) Plants such as oilseed rape plants, producing oil having a low    linolenic acid content as described in U.S. Pat. No. 6,270,828, U.S.    Pat. No. 6,169,190, or U.S. Pat. No. 5,965,755-   c) Plant such as oilseed rape plants, producing oil having a low    level of saturated fatty acids as described e.g. in U.S. Pat. No.    5,434,283 or U.S. patent application Ser. No. 12/668,303

Plants or plant cultivars (that can be obtained by plant biotechnologymethods such as genetic engineering) which may also be treated accordingto the invention are plants, such as oilseed rape or related Brassicaplants, with altered seed shattering characteristics. Such plants can beobtained by genetic transformation, or by selection of plants contain amutation imparting such altered seed shattering characteristics andinclude plants such as oilseed rape plants with delayed or reduced seedshattering as described in U.S. Patent Application 61/135,230, WO2009/068313 and WO 2010/006732.

Plants or plant cultivars (that can be obtained by plant biotechnologymethods such as genetic engineering) which may also be treated accordingto the invention are plants, such as Tobacco plants, with alteredpost-translational protein modification patterns, for example asdescribed in WO 2010/121818 and WO 2010/145846.

Particularly useful transgenic plants which may be treated according tothe invention are plants containing transformation events, orcombination of transformation events, that are the subject of petitionsfor nonregulated status, in the United States of America, to the Animaland Plant Health Inspection Service (APHIS) of the United StatesDepartment of Agriculture (USDA) whether such petitions are granted orare still pending. At any time this information is readily availablefrom APHIS (4700 River Road, Riverdale, Md. 20737, USA), for instance onits internet site (URL http://www.aphis.usda.gov/brs/not_reg.html). Onthe filing date of this application the petitions for nonregulatedstatus that were pending with APHIS or granted by APHIS were those whichcontains the following information:

-   -   Petition: the identification number of the petition. Technical        descriptions of the transformation events can be found in the        individual petition documents which are obtainable from APHIS,        for example on the APHIS website, by reference to this petition        number. These descriptions are herein incorporated by reference.    -   Extension of Petition: reference to a previous petition for        which an extension is requested.    -   Institution: the name of the entity submitting the petition.    -   Regulated article: the plant species concerned.    -   Transgenic phenotype: the trait conferred to the plants by the        transformation event.    -   Transformation event or line: the name of the event or events        (sometimes also designated as lines or lines) for which        nonregulated status is requested.    -   APHIS documents: various documents published by APHIS in        relation to the Petition and which can be requested with APHIS.

Additional particularly useful plants containing single transformationevents or combinations of transformation events are listed for examplein the databases from various national or regional regulatory agencies(see for example http://gmoinfo.jrc.it/gmp_browse.aspx andhttp://www.agbios.com/dbase.php).

Application Rates and Timing

When using the inventive active ingredients as fungicides, theapplication rates can be varied within a relatively wide range,depending on the kind of application. The application rate of theinventive active ingredients is

-   -   in the case of treatment of plant parts, for example leaves:        from 0.1 to 10 000 g/ha, preferably from 10 to 1000 g/ha, more        preferably from 10 to 800 g/ha, even more preferably from 50 to        300 g/ha (in the case of application by watering or dripping, it        is even possible to reduce the application rate, especially when        inert substrates such as rockwool or perlite are used);    -   in the case of seed treatment: from 2 to 200 g per 100 kg of        seed, preferably from 3 to 150 g per 100 kg of seed, more        preferably from 2.5 to 25 g per 100 kg of seed, even more        preferably from 2.5 to 12.5 g per 100 kg of seed;    -   in the case of soil treatment: from 0.1 to 10 000 g/ha,        preferably from 1 to 5000 g/ha.

These application rates are merely by way of example and are notlimiting for the purposes of the invention.

The inventive active ingredients or compositions comprising a compoundaccording to formula (I) can thus be used to protect plants from attackby the pathogens mentioned for a certain period of time after treatment.The period for which protection is provided extends generally for 1 to28 days, preferably for 1 to 14 days, more preferably for 1 to 10 days,most preferably for 1 to 7 days, after the treatment of the plants withthe active ingredients, or for up to 200 days after a seed treatment.

The plants listed can particularly advantageously be treated inaccordance with the invention with the compounds of the general formula(I) and the inventive compositions. The preferred ranges stated abovefor the active ingredients or compositions also apply to the treatmentof these plants. Particular emphasis is given to the treatment of plantswith the compounds or compositions specifically mentioned in the presenttext.

The invention is illustrated by the examples below. However, theinvention is not limited to the examples.

EXAMPLES Preparation Examples Preparation of Compounds of the Formula(I-4) According to Process H Preparation of1-(3-chloropyridin-4-yl)-3,3-dimethyl-2-(1H-1,2,4-triazol-1-ylmethyl)butan-2-ol(I-4)

To a solution of 1H-1,2,4-triazole (3.1 g, 3 eq, 45 mmol) in 6 mLdimethylformamide was added potassium carbonate (5.8 g, 2.8 eq, 42 mmol)and a solution of 4-[(2-tert-butyloxiran-2-yl)methyl]-3-chloropyridine(3.7 g, 1 eq, 15 mmol) in 4 mL dimethylformamide. Thereafter 25 mgpotassium tert butylate was added and the mixture was stirred for 5 h at50° C. Thereafter the reaction mixture was evaporated in vacuo andtreated with ethyl acetate. After filtration and evaporation of thesolvent the crude product was purified by chromatography over silicausing a 1:1 mixture of ethyl acetate/cyclohexane as eluent. Afterevaporation of the solvent 2.05 g (41%) of1-(3-chloropyridin-4-yl)-3,3-dimethyl-2-(1H-1,2,4-triazol-1-ylmethyl)butan-2-olwere obtained as solid.

MS (ESI): 295.1 ([M+H]⁺)

Preparation of Intermediates of the Formula (XII-4) According to ProcessD Preparation of 3-[(2-tert-butyloxiran-2-yl)methyl]-2-chloropyridine(XII-4)

To a mixture of trimethylsulfoxonium chloride (18.4 g, 1.1 eq, 1.1 mmol)and 1-(2-chloropyridin-3-yl)-3,3-dimethylbutan-2-one (29.9 g, 1.0 eq,130 mmol) in 65 mL toluene was added under stirring sodium hydroxide(34.6 g, 3 eq, 45% weight in H₂O) and hexadecyltrimethylammoniumbromide(947 mg, 0.02 eq). The obtained mixture was stirred for 6 h at 40° C.The obtained mixture was diluted with water extracted with ethyl acetateand the phases were separated. The organic phase was evaporated andpurified by column chromatography over silica gel (eluentcyclohexane/ethyl acetate gradient). After evaporation of the solvent6.0 g (18%) of 3-[(2-tert-butyloxiran-2-yl)methyl]-2-chloropyridine wereobtained as colourless oil.

MS (ESI): 226.1 ([M+H]⁺)

Preparation of Intermediates of the Formula (XII-5) According to ProcessF Preparation of 4-[(2-tert-butyloxiran-2-yl)methyl]-3-chloropyridine(XII-5)

To a solution of lithium diisopropylamide (6 mL, 2M in THF, 12 mmol) in5 mL THF at −70° C. was added under argon a solution of3-chloro-4-methylpyridine (1.28 g, 1 eq, 10 mmol) in 5 mL THF. Themixture was stirred for 5 min at −70° C. and then allowed to reach −30°C. Thereafter the mixture was cooled down to −70° C. and a solution of1-chloro-3,3-dimethylbutan-2-one (2.7 g, 2 eq, 20 mmol) in 5 mL THF wasadded. Then the mixture was allowed to reach ambient temperature andstirred for 1 h. Thereafter the mixture was cooled to 0° C. andsaturated aqueous ammonium chloride solution was added. After extractionwith ethyl acetate and evaporation of the solvent the crude material waspurified via column chromatography over silica gel (eluentcyclohexane/ethyl acetate gradient). After evaporation of the solvent 2g (81%) of 4-[(2-tert-butyloxiran-2-yl)methyl]-3-chloropyridine wereobtained as colourless oil.

MS (ESI): 226.1 ([M+H]⁺)

Preparation of Intermediates of the Formula (V-4) According to Process APreparation of 1-(2-chloropyridin-3-yl)-3,3-dimethylbutan-2-one (V-4)

To a suspension of zinc dust (60.5 g, 3 eq) and LiCl (39.4 g, 3 eq) indegassed THF (1100 mL) was added dropwise under argon a solution of2-chloro-3-chloromethylpyridine (50 g, 1 eq) in THF. The resultingreaction mixture was heated to 75° C. for 2 h. The reaction mixture wascooled and Pd(PPh₃)₂Cl₂ (8.7 g, 0.04 eq.) and pivaloyl chloride (37.25g, 1.0 eq.) was added dropwise over a period of 10 min. Then thereaction mixture was heated to 70° C. for 1 h. The progress of thereaction was monitored by TLC. After completion of reaction (TLC), thereaction mixture was concentrated under reduced pressure, diluted withethyl acetate and filtered through Celite bed. The filtrate wasconcentrated under reduced pressure to get the crude compound which waspurified over silica gel (100-200 mesh) column chromatography (eluent10% ethyl acetate/pet ether) and 24.2 g (36%) of1-(2-chloropyridin-3-yl)-3,3-dimethylbutan-2-one were obtained as paleyellow solid.

MS (ESI): 212.0 ([M+H]⁺)

Preparation of Intermediates of the Formula (V-4) According to Process BPreparation of 1-(2-chloropyridin-3-yl)-3,3-dimethylbutan-2-one (V-4)

To a solution of lithium diisopropylamide (102 mL, 1.2 eq, 204 mmol, 2Min THF) in 150 mL THF at −70° C. was added under argon a solution of2-chloro-3-methylpyridine (21.6 g, 1 eq, 170 mmol) in 50 mL THF. Themixture was stirred for 50 min at −70° C. and then allowed to reach −30°C. In a separate flask a solution of ethyl pivalate (33.2 g, 1.5 eq, 255mmol) in 150 mL THF was cooled to −30° C. To this solution themethylpyridine solution was slowly added at −30° C. Thereafter themixture was allowed to reach ambient temperature and stirred for 1 h.Thereafter the mixture is cooled to 0° C. and saturated aqueous ammoniumchloride solution was added. After extraction with ethyl acetate andevaporation of the solvent the crude material was purified via columnchromatography over silica gel (eluent cyclohexane/ethyl acetategradient). After evaporation of the solvent 13.5 g (35%) of1-(2-chloropyridin-3-yl)-3,3-dimethylbutan-2-one were obtained ascolourless oil.

The exemplary compounds according to the invention listed in Table 1, 2and 3 have been synthesized analogous to the above mentioned processes.

The following Table illustrates in a non-limiting manner examples ofcompounds according to formula (I).

TABLE 1 Ex No R¹ R² X LogP I-1 tert-butyl H quinolin-3-yl 1.18^([a]) I-2tert-butyl H 6-chloropyridin-3-yl 1.98^([b]); 1.98^([a]) I-3 tert-butylH 2-chloropyridin-3-yl 1.90^([b]); 1.94^([a]) I-4 tert-butyl H3-chloropyridin-4-yl 1.74^([a]) I-5 2-methylbutan-2-yl H3-chloropyridin-4-yl 2.13^([a]) I-6 tert-butyl H 3-fluoropyridin-4-yl1.41^([a]) I-7 2-methylbutan-2-yl H 3-fluoropyridin-4-yl 1.73^([a]) I-8tert-butyl H quinolin-2-yl 1.51^([a]) I-9 tert-butyl H2,6-dichloropyridin-4-yl 2.64^([a]) I-10 tert-butyl H quinolin-4-yl1.17^([a]) I-11 tert-butyl H 4,6-dichloropyridin-2-yl 2.86^([a]) I-12tert-butyl H 5,6-dichloropyridin-2-yl 2.78^([a]) I-13 tert-butyl H6-chloropyridin-2-yl 2.30^([a]) I-14 2-methylbutan-2-yl H2-chloropyridin-4-yl 2.27^([a]) I-15 tert-butyl H 2-chloropyridin-4-yl1.93^([a]) I-16 tert-butyl H 2-chloro-5-fluoropyridin-4-yl 2.16^([a])I-17 tert-butyl H 6-chloropyrazin-2-yl 1.89^([a]) I-18 tert-butyl H3-chloropyrazin-2-yl 2.01^([a]) I-19 tert-butyl H6-chloro-5-methylpyrazin-2-yl 2.10^([a]) I-20 tert-butyl H3-chloro-5-methylpyrazin-2-yl 2.21^([a]) I-21 tert-butyl H pyrazin-2-yl1.39^([a]) I-22 tert-butyl H 4-chloropyridin-2-yl 1.87^([a]) I-23tert-butyl H 6-methylpyridin-2-yl 0.63^([a]) I-24 tert-butyl CO₂Et2-chloropyridin-3-yl 2.56^([b]); 2.67^([a]) I-25 tert-butyl H6-(4-chlorophenoxy)pyrazin-2-yl 2.98^([a]) I-26 2-methoxypropan-2-yl H3-chloropyridin-4-yl 1.48^([a]) I-27 tert-butyl H2-chloro-3-fluoropyridin-4-yl 2.16^([a]) I-28 tert-butyl H3,5-dichloropyridin-4-yl 2.34^([a]) I-29 tert-butyl H5-chloro-2-fluoropyridin-4-yl 2.39^([a]) I-30 cyclopropylmethyl H3-chloropyridin-4-yl 1.43^([a]) I-31 3-methylbutan-1-yl H3-chloropyridin-4-yl 2.00^([a]) I-32 2-ethoxypropan-2-yl H3-chloropyridin-4-yl 2.04^([b]); 1.90^([a]) I-33 tert-butyl H3,6-dichloropyridin-2-yl 2.82^([a])

The following Table 2 illustrates in a non-limiting manner examples ofcompounds according to formula (V).

TABLE 2 Ex No R¹ X LogP V-1 tert-butyl 3,5-dichloropyridin-2-yl3.33^([a]) V-2 tert-butyl quinolin-3-yl 1.60^([a]) V-3 tert-butyl6-chloropyridin-3-yl 2.47^([a]) V-4 tert-butyl 2-chloropyridin-3-yl2.34^([a]) V-5 3-methylpentan-3-yl 3-chloropyridin-4-yl 3.04^([a]) V-62,3-dimethylbutan-2-yl 3-chloropyridin-4-yl 3.00^([a]) V-7 tert-butylpyridin-3-yl 1.71^([b]); 0.41^([a]) V-8 tert-butyl pyridin-4-yl1.75^([b]); 0.35^([a]) V-9 tert-butyl pyrimidin-5-yl V-10 tert-butyl3-chloropyridin-4-yl

The following Table 3 illustrates in a non-limiting manner examples ofcompounds according to formula (XII).

TABLE 3 Ex No R¹ X LogP XII-1 tert-butyl 3,5-dichloropyridin-2-yl4.06^([a]) XII-2 tert-butyl quinolin-3-yl 1.86^([a]) XII-3 tert-butyl6-chloropyridin-3-yl XII-4 tert-butyl 2-chloropyridin-3-yl 2.96^([b]);2.97^([a]) XII-5 tert-butyl 3-chloropyridin-4-yl 2.80^([a]) XII-6tert-butyl pyridin-3-yl XII-7 tert-butyl 3-fluoropyridin-4-yl 2.31^([a])XII-8 2-methylbutan-2-yl 3-fluoropyridin-4-yl 2.76^([a]) XII-92,3-dimethylbutan-2-yl 3-fluoropyridin-4-yl 3.19^([a]) XII-102-methylbutan-2-yl 2-chloropyridin-4-yl 3.51^([a]) XII-112,3-dimethylbutan-2-yl 2-chloropyridin-4-yl 3.94^([a]) XII-12 tert-butyl2-chloropyridin-4-yl 3.06^([a]) XII-13 2,3-dimethylbutan-2-yl2-chloro-5-fluoropyridin-4-yl 4.34^([a]) XII-14 2-methylbutan-2-yl2-chloro-5-fluoropyridin-4-yl 3.89^([a]) XII-15 tert-butyl2-chloro-5-fluoropyridin-4-yl 3.42^([a]) XII-16 2,3-dimethylbutan-2-yl3-chloropyridin-4-yl 3.75^([a]) XII-17 2-methylbutan-2-yl3-chloropyridin-4-yl 3.33^([a]) XII-18 tert-butyl5-chloro-2-fluoropyridin-4-yl 3.65^([a]) XII-19 2-methylbutan-2-yl5-chloro-2-fluoropyridin-4-yl 4.17^([a]) XII-20 tert-butyl2-chloro-3-fluoropyridin-4-yl 3.37^([a]) XII-21 tert-butyl3,5-dichloropyridin-4-yl 3.89^([a]) XII-22 2-methylbutan-2-yl3,5-dichloropyridin-4-yl 4.41^([a]) XII-23 2-methylpentan-2-yl3-chloropyridin-4-yl 2.03^([a])

Measurement of Log P values for Tables 1, 2 and 3 was performedaccording to EEC directive 79/831 Annex V.A8 by HPLC (High PerformanceLiquid Chromatography) on reversed phase columns with the followingmethods:

^([a]) Measurement of LC-MS was done at pH 2.7 with 0.1% formic acid inwater and with acetonitrile (contains 0.1% formic acid) as eluent with alinear gradient from 10% acetonitrile to 95% acetonitrile.

^([b]) Measurement with LC-MS was done at pH 7.8 with 0.001 molarammonium hydrogen carbonate solution in water as eluent with a lineargradient from 10% acetonitrile to 95% acetonitrile.

Calibration was done with straight-chain alkan2-ones (with 3 to 16carbon atoms) with known Log P values (measurement of Log P values usingretention times with linear interpolation between successive alkanones)Lambda-max-values were determined using UV-spectra from 200 nm to 400 nmand the peak values of the chromatographic signals.

1H-NMR Data and 1H-NMR-Peak List

1H-NMR data of selected examples from Tables 1, 2 and 3 are eitherwritten in classical form (d-value in ppm, number of H-atoms, multipletsplitting) or as 1H-NMR-peak list.

In the 1H-NMR-peak list to each signal peak are listed the 6-value inppm and the signal intensity in round brackets. Between theδ-value—signal intensity pairs are semicolons as delimiters.

The peak list of an example has therefore the form:

δ₁ (intensity₁); δ₂ (intensity₂); . . . ; δ₁(intensity); . . . ;δ_(n)(intensity_(n))

Intensity of sharp signals correlates with the height of the signals ina printed example of a NMR spectrum in cm and shows the real relationsof signal intensities. From broad signals several peaks or the middle ofthe signal and their relative intensity in comparison to the mostintensive signal in the spectrum can be shown.

For calibrating chemical shift for 1H spectra, we use tetramethylsilaneand/or the chemical shift of the solvent used, especially in the case ofspectra measured in DMSO. Therefore in NMR peak lists, tetramethylsilanepeak can occur but not necessarily.

The 1H-NMR peak lists are similar to classical 1H-NMR prints andcontains therefore usually all peaks, which are listed at classicalNMR-interpretation.

Additionally they can show like classical 1H-NMR prints signals ofsolvents, stereoisomers of the target compounds, which are also objectof the invention, and/or peaks of impurities.

To show compound signals in the delta-range of solvents and/or water theusual peaks of solvents, for example peaks of DMSO in DMSO-D₆ and thepeak of water are shown in our 1H-NMR peak lists and have usually onaverage a high intensity.

The peaks of stereoisomers of the target compounds and/or peaks ofimpurities have usually on average a lower intensity than the peaks oftarget compounds (for example with a purity >90%).

Such stereoisomers and/or impurities can be typical for the specificpreparation process. Therefore their peaks can help to recognize thereproduction of our preparation process via“side-products-fingerprints”.

An expert, who calculates the peaks of the target compounds with knownmethods (MestreC, ACD-simulation, but also with empirically evaluatedexpectation values) can isolate the peaks of the target compounds asneeded optionally using additional intensity filters. This isolationwould be similar to relevant peak picking at classical 1H-NMRinterpretation.

Further details of NMR-data description with peak lists you find in thepublication “Citation of NMR Peaklist Data within Patent Applications”of the Research Disclosure Database Number 564025.

1H-NMR Data for Compounds in Table 1 Written in Classical Form

Ex-no NMR I-2 1H-NMR (400 MHz, d3-CD3CN): δ = 8.08-8.07 (m, 2H), 7.65(s, 1H), 7.55-7.52 (dd, 1H), 7.16-7.14 (d, 1H), 4.26 (s, 2H), 3.92 (s,1H), 3.01 (d, 1H), 2.82 (d, 1H) ppm I-3 1H-NMR (400 MHz, d3-CD3CN): δ =8.16-8.14 (dd, 1H), 8.06 (s, 1H), 7.80-7.78 (dd, 1H), 7.66 (s, 1H),7.16-7.13 (dd, 1H), 4.42 (d, 1H), 4.15 (d, 1H), 3.23 (d, 1H), 3.05 (d,1H), 0.98 (s, 9H) ppm I-4 1H-NMR (400 MHz, d3-CD3CN): δ = 8.41 (s, 1H),8.24 (d, 1H), 8.08 (s, 1H), 7.67 (s, 1H), 7.39 (d, 1H), 4.40 (d, 1H),4.32 (s, 1H), 4.15 (d, 1H), 3.22 (d, 1H), 3.06 (d, 1H), 0.97 (s, 9H) ppmI-5 1H-NMR (400 MHz, DMSO-d6): δ = 8.49 (s, 1H), 8.37 (s, 1H), 8.31 (d,1H), 7.81 (s, 1H), 7.55 (d, 1H), 4.93 (s, 1H), 4.36 (d, 1H), 4.08 (d,1H), 3.13 (d, 1H), 3.02 (d, 1H), 1.42-1.37 (q, 2H), 0.83-0.74 (m, 9H)ppmNMR-Peak Lists for Compounds in Table 1

Example I-1: ¹H-NMR(300.2 MHz, CDCl3): δ = 8.730(0.8); 8.723(0.9);8.061(0.4); 8.032(0.5); 7.931(1.5); 7.831(0.6); 7.825(0.6); 7.722(0.4);7.695(0.6); 7.690(0.4); 7.685(0.3); 7.673(1.6); 7.667(0.6); 7.662(0.6);7.639(0.4); 7.538(0.4); 7.534(0.4); 7.514(0.3); 7.511(0.6); 7.507(0.3);7.264(2.6); 4.383(0.5); 4.336(0.9); 4.205(1.0); 4.158(0.6); 3.872(1.5);3.314(0.5); 3.267(0.6); 2.953(0.7); 2.920(0.7); 2.881(0.6); 2.880(0.6);2.872(0.6); 1.710(1.0); 1.058 (16.0); 0.000(1.5) Example I-6:¹H-NMR(400.0 MHz, DMSO): δ = 8.420(2.5); 8.384(1.3); 8.380(1.2);8.233(0.8); 8.232(0.8); 8.221(0.8); 8.219(0.8); 7.868(2.6); 7.471(0.5);7.459(0.6); 7.455(0.6); 7.443(0.5); 4.854(2.9); 4.317(0.6); 4.281(1.2);4.221(1.2); 4.184(0.6); 3.334(22.8); 2.946(2.5); 2.543(8.7); 2.512(2.8);2.508(5.6); 2.503(7.2); 2.499(5.1); 2.494(2.4); 0.890(16.0); 0.000(2.8)Example I-7: ¹H-NMR(400.0 MHz, DMSO): δ = 8.409(7.0); 8.371(3.6);8.366(3.6); 8.219(2.3); 8.217(2.3); 8.206(2.4); 8.205(2.3); 7.851(7.2);7.439(1.5); 7.426(1.8); 7.423(1.8); 7.410(1.4); 4.822(6.9); 4.323(1.7);4.287(3.4); 4.228(3.5); 4.191(1.7); 3.328(57.9); 2.945(5.4);2.542(31.1); 2.525(0.6); 2.511(12.8); 2.507(25.8); 2.502(33.8);2.498(24.0); 2.493(11.3); 1.414(0.9); 1.396(3.2); 1.377(3.5);1.359(1.1); 0.826(5.4); 0.819(16.0); 0.808(9.2); 0.789(3.7);0.771(15.5); 0.000(8.2) Example I-8: ¹H-NMR(300.2 MHz, CDCl3): δ =8.240(0.8); 8.137(1.6); 8.007(0.6); 7.979(0.7); 7.865(0.4); 7.837(0.5);7.741(0.4); 7.714(0.5); 7.667(0.4); 7.662(0.5); 7.514(1.6); 7.504(0.4);7.500(0.4); 7.480(0.3); 7.477(0.6); 7.473(0.3); 7.265(1.5); 7.156(0.9);7.128(0.8); 4.475(0.4); 4.429(1.3); 4.393(1.0); 3.301(0.5); 3.248(0.8);3.039(1.0); 2.986(0.7); 1.056(16.0); 0.000(1.1) Example I-9:¹H-NMR(300.2 MHz, CDCl3): δ = 8.027(1.7); 7.800(1.6); 7.274(0.8);7.022(3.5); 4.337(0.5); 4.290(0.9); 4.187(1.1); 4.151(1.6); 4.140(0.7);3.074(0.5); 3.028(0.7); 2.642(0.8); 2.595(0.7); 1.025(16.0); 0.000(0.5)Example I-10: ¹H-NMR(300.2 MHz, CDCl3): δ = 8.703(0.9); 8.690(0.8);8.141(0.9); 8.112(1.0); 8.087(0.8); 8.060(0.8); 7.709(0.5); 7.686(0.8);7.660(0.5); 7.615(1.9); 7.589(0.6); 7.561(0.9); 7.546(3.3); 7.366(1.3);7.351(1.1); 7.291(0.5); 4.417(1.7); 4.363(0.9); 4.315(1.2); 4.041(1.2);3.994(0.9); 3.444(2.9); 2.035(0.6); 1.251(0.4); 1.080(16.0) ExampleI-11: ¹H-NMR(300.2 MHz, CDCl3): δ = 8.100(1.4); 7.707(1.5); 7.265(2.4);7.115(0.8); 7.111(0.8); 6.969(0.8); 6.965(0.8); 6.036(1.5); 4.483(0.5);4.436(0.9); 4.339(0.8); 4.292(0.4); 3.044(0.4); 2.993(0.6); 2.846(0.9);2.796(0.6); 2.046(0.4); 1.637(0.7); 1.044(16.0); 0.000(1.7) ExampleI-12: ¹H-NMR(300.2 MHz, CDCl3): δ = 8.158(1.6); 7.698(1.6); 7.600(1.1);7.573(1.2); 7.284(0.5); 6.982(0.9); 6.955(0.8); 5.832(1.3); 4.486(0.5);4.439(1.0); 4.333(0.9); 4.286(0.5); 3.027(0.4); 2.976(0.8); 2.879(1.0);2.828(0.5); 1.224(0.3); 1.020(16.0); 0.000(0.3) Example I-13:¹H-NMR(400.1 MHz, DMSO): δ = 8.470(2.2); 7.837(2.1); 7.758(0.6);7.738(1.2); 7.719(0.8); 7.406(0.9); 7.387(0.8); 7.331(0.9); 7.311(0.8);5.310(2.5); 4.364(0.4); 4.328(1.3); 4.297(1.2); 4.261(0.4); 3.312(6.4);3.029(0.6); 2.993(1.0); 2.901(1.1); 2.891(1.7); 2.865(0.6); 2.732(1.4);2.511(2.4); 2.506(4.7); 2.502(6.2); 2.498(4.4); 2.493(2.1); 0.878(16.0);0.000(1.1) Example I-14: ¹H-NMR(400.0 MHz, DMSO): δ = 8.382(5.5);8.182(2.5); 8.170(2.5); 7.884(5.9); 7.351(3.2); 7.307(1.8); 7.304(1.6);7.294(1.7); 7.291(1.6); 4.809(5.7); 4.203(4.8); 3.329(30.1); 2.914(6.4);2.542(31.9); 2.525(0.3); 2.520(0.6); 2.512(7.7); 2.507(15.7);2.503(20.6); 2.498(14.6); 2.494(6.8); 1.392(0.4); 1.373(1.2);1.362(1.2); 1.354(1.3); 1.344(1.2); 1.336(0.5); 1.327(0.5); 0.819(3.2);0.800(16.0); 0.781(3.3); 0.772(11.4) Example I-15: ¹H-NMR(400.0 MHz,DMSO): δ = 8.408(2.8); 8.207(1.2); 8.194(1.3); 7.908(3.0); 7.403(1.5);7.354(0.9); 7.351(0.8); 7.341(0.8); 7.338(0.8); 4.851(2.8); 4.192(3.1);3.339(4.8); 2.970(0.4); 2.936(1.4); 2.916(1.3); 2.882(0.3); 2.549(12.7); 2.519(1.8); 2.515(3.7); 2.510(4.9); 2.505(3.5); 2.501(1.6);0.879(16.0) Example I-16: ¹H-NMR(400.0 MHz, DMSO): δ = 8.411(2.2);8.254(1.4); 8.252(1.4); 7.841(2.2); 7.464(1.0); 7.451(1.0); 4.945(2.3);4.273(1.4); 4.255(1.4); 3.340(123.4); 2.954(2.6); 2.542(10.5);2.507(23.2); 2.503(29.4); 2.498(21.8); 1.177(0.9); 0.913(16.0);0.000(0.6) Example I-17: ¹H-NMR(300.2 MHz, CDCl3): δ = 8.344(1.2);8.287(1.3); 8.112(1.3); 7.634(1.4); 7.262(6.7); 5.481(1.7); 4.515(0.5);4.468(0.9); 4.362(0.7); 4.314(0.4); 4.134(0.5); 4.110(0.6); 3.041(0.7);2.986(1.0); 2.935(0.4); 2.046(2.5); 1.576(1.8); 1.284(0.7); 1.260(1.4);1.236(0.7); 1.066(16.0); 0.000(5.1) Example I-18: ¹H-NMR(300.2 MHz,CDCl3): δ = 8.160(1.3); 8.146(0.7); 8.137(0.7); 8.028(1.0); 8.019(0.9);7.476(1.4); 7.264(3.9); 6.648(1.6); 5.302(1.1); 4.487(0.3); 4.440(1.1);4.406(0.9); 3.239(1.2); 3.230(1.0); 2.046(0.4); 1.604(0.8); 1.260(0.3);1.254(0.3); 1.092(16.0); 0.000(2.8) Example I-19: ¹H-NMR(499.9 MHz,CDCl3): δ = 8.163(1.6); 8.116(1.7); 7.649(1.6); 7.277(0.5); 5.473(1.6);4.494(0.7); 4.466(1.0); 4.338(0.9); 4.310(0.6); 3.018(0.4); 2.988(0.8);2.935(1.1); 2.905(0.5); 2.566(4.8); 1.049(16.0); 0.000(0.4) ExampleI-20: ¹H-NMR(300.2 MHz, CDCl3): δ = 8.168(1.7); 7.907(1.5); 7.518(1.7);7.274(0.8); 6.640(1.7); 4.469(0.3); 4.422(1.4); 4.396(1.3); 3.164(1.9);2.466(4.6); 1.255(0.5); 1.072(16.0); 0.000(0.6) Example I-21:¹H-NMR(300.2 MHz, CDCl3): δ = 8.358(0.8); 8.354(0.8); 8.338(0.6);8.330(0.6); 8.169(0.5); 8.164(0.6); 8.160(0.6); 8.155(0.5); 8.146(0.4);8.066(1.4); 7.962(0.4); 7.575(1.4); 7.262(13.3); 6.484(1.4); 5.196(1.3);4.482(0.4); 4.435 (1.0); 4.362(0.7); 4.315(0.3); 3.093(0.6); 2.963(0.9);2.911(0.5); 1.575(4.9); 1.283(7.8); 1.073(16.0); 0.000(9.8); −0.011(0.4)Example I-22: ¹H-NMR(400.1 MHz, DMSO): δ = 8.416(2.2); 8.362(1.0);8.348(1.1); 7.808(2.1); 7.491(1.0); 7.486(1.1); 7.364(0.7); 7.359(0.6);7.351(0.7); 7.345(0.6); 6.014(2.4); 4.343(0.3); 4.307(1.3); 4.288(1.3);4.252(0.3); 3.318(10.3); 3.074 (0.5); 3.037(0.9); 2.926(1.0);2.889(0.6); 2.530(0.3); 2.517(3.9); 2.512(7.8); 2.508(10.5); 2.503(7.6);2.499(3.8); 0.901(16.0) Example I-23: ¹H-NMR(300.2 MHz, DMSO): δ =8.369(2.2); 7.728(2.1); 7.587(0.5); 7.561(1.1); 7.535(0.7); 7.115(0.7);7.089(0.6); 7.048(0.7); 7.023(0.7); 6.999(2.1); 4.279(1.3); 4.261(1.4);3.330(5.2); 3.026(0.5); 2.976(0.8); 2.835(0.9); 2.785(0.6); 2.510(0.6);2.503(0.8); 2.497(0.6); 2.359(5.4); 1.172(0.6); 1.118(0.6); 0.892(16.0);0.000(0.5) Example I-24: ¹H-NMR(400.0 MHz, CD3CN): δ = 8.226(0.5);8.221(0.5); 8.214(0.5); 8.209(0.5); 8.158(1.6); 7.761(2.1); 7.741(0.6);7.737(0.5); 7.236(0.6); 7.225(0.6); 7.217(0.5); 7.206(0.5); 5.449(1.1);4.968(0.6); 4.930(1.3); 4.878(1.3); 4.840(0.6); 4.133(0.6); 4.116(1.7);4.098(1.7); 4.080(0.6); 3.768(0.7); 3.730(0.9); 3.414(1.0); 3.376(0.8);2.181(4.0); 1.959(0.4); 1.953(1.6); 1.947(2.8); 1.941(3.6); 1.935(2.4);1.929(1.2); 1.273(1.9); 1.256(3.6); 1.238(1.8); 0.987(16.0); 0.000(4.4)Example I-25: ¹H-NMR(300.2 MHz, CDCl3): δ = 8.178(1.3); 8.057(1.4);7.829(1.7); 7.658(1.7); 7.446(1.5); 7.438(0.5); 7.423(0.5); 7.416(1.8);7.263(5.7); 7.082(1.8); 7.075(0.6); 7.060(0.5); 7.052(1.5); 5.081(1.6);4.413(0.5); 4.366(0.9); 4.251(0.8); 4.205(0.5); 2.832(0.8); 2.790(1.0);2.739(0.3); 1.599(3.6); 0.967(16.0); 0.000(3.6) Example I-26:¹H-NMR(400.0 MHz, CD3CN): δ = 8.450(3.8); 8.273(2.2); 8.260(2.3);8.112(2.6); 8.085(3.5); 7.714(3.4); 7.447(2.1); 7.434(2.0); 4.494(2.0);4.457(2.5); 4.167(2.6); 4.131(2.1); 3.298(0.5); 3.187(0.4); 3.159(16.0);3.151(5.2); 3.146 (4.6); 3.111(0.4); 2.891(0.4); 2.774(0.4); 2.473(0.4);2.469(0.4); 2.380(0.5); 2.334(0.5); 2.306(0.5); 2.299(0.5); 2.279(0.5);2.268(0.5); 2.230(0.5); 2.180(0.4); 2.141(0.4); 2.122(0.4); 2.116(0.4);2.110(0.4); 2.103(0.3); 1.966(0.7); 1.960(1.2); 1.954(5.1); 1.948(9.0);1.942(11.9); 1.936(8.4); 1.930(4.5); 1.345(0.9); 1.161(12.0);1.137(11.9); 0.000(4.2) Example I-27: ¹H-NMR(400.0 MHz, DMSO): δ =8.412(2.9); 8.047(1.5); 8.034(1.6); 7.835(2.8); 7.467(0.7); 7.454(1.3);7.442(0.6); 4.931(2.8); 4.258(2.8); 3.352(8.9); 3.027(1.6); 3.015(1.4);2.548(10.6); 2.513(2.0); 2.508(2.6); 2.504(1.9); 0.956 (1.0);0.934(0.9); 0.917(16.0); 0.000(0.5) Example I-28: ¹H-NMR(400.0 MHz,DMSO): δ = 8.495(5.6); 8.335(2.8); 8.313(0.5); 7.753(2.8); 5.010(2.7);4.584(1.0); 4.548(1.1); 4.104(1.2); 4.068(1.1); 3.415(0.6);3.341(997.0); 3.286(2.2); 3.266(1.9); 3.241(0.3); 3.231(0.6);2.676(1.0); 2.672(1.4); 2.668(1.0); 2.542(43.8); 2.525(3.7);2.507(174.3); 2.503(222.2); 2.498(163.1); 2.462(0.5); 2.334(1.1);2.330(1.4); 2.325(1.1); 1.235(1.2); 0.933(16.0); 0.000(1.5) ExampleI-29: ¹H-NMR(400.1 MHz, DMSO): δ = 8.400(2.3); 8.207(1.5); 7.792(2.3);7.293(1.1); 7.289(1.1); 5.020(2.3); 4.370(0.7); 4.333(0.9); 4.171(1.0);4.134(0.7); 3.313(7.1); 3.195(0.6); 3.159(1.0); 3.067(0.9); 3.031(0.6);2.511(2.5); 2.506(5.1); 2.502(6.9); 2.497(5.1); 2.493(2.6); 2.074(0.9);0.917(16.0) Example I-30: ¹H-NMR(400.0 MHz, DMSO): δ = 8.567(14.3);8.426(8.5); 8.413(9.1); 8.405(16.0); 7.981(15.6); 7.586(7.1);7.573(6.8); 5.081(14.2); 4.459(5.0); 4.423(6.5); 4.216(6.6); 4.181(5.1);3.386(0.6); 3.375(1.0); 3.344(290.9); 3.307(0.4); 3.029(3.7);2.994(7.5); 2.941(7.5); 2.906(3.6); 2.677(0.3); 2.673(0.5); 2.668(0.4);2.543(66.4); 2.526 (1.2); 2.512(26.4); 2.508(54.3); 2.504(72.0);2.499(52.5); 2.495(25.8); 2.330(0.4); 2.326(0.3); 1.357 (1.0);1.340(1.1); 1.321(4.2); 1.304(7.4); 1.286(4.4); 1.267(1.0); 1.250(1.2);1.234(0.3); 0.899(0.6); 0.885(1.4); 0.868(2.0); 0.855(1.4); 0.853(1.4);0.837(0.7); 0.499(0.5); 0.479(2.0); 0.466(5.3); 0.456(3.0); 0.447(4.8);0.436(2.1); 0.420(0.5); 0.415(0.6); 0.125(1.0); 0.113(2.2); 0.101(3.0);0.094(2.2); 0.090(2.3); 0.085(3.2); 0.078(2.3); 0.071(2.9); 0.059(2.1);0.047(1.0); 0.008(0.6); 0.000(16.5); −0.009(0.7) Example I-31:¹H-NMR(400.0 MHz, DMSO): δ = 20.011(0.4); 8.571(10.9); 8.428(6.1);8.416(6.9); 8.409(12.4); 7.977(11.8); 7.571(5.5); 7.559(5.4);7.284(0.7); 7.259(0.7); 5.015(11.3); 4.300(3.4); 4.264(5.2); 4.147(5.2);4.111(3.5); 3.816(0.4); 3.797 (0.3); 3.504(0.3); 3.335(2768.3);2.992(3.5); 2.958(5.5); 2.868(5.4); 2.833(3.3); 2.712(0.5); 2.675(4.3);2.671(5.7); 2.667(4.3); 2.541(57.6); 2.506(671.2); 2.502(871.7);2.498(636.4); 2.368(0.4); 2.333(4.1); 2.329(5.4); 2.324(4.0);2.289(0.4); 1.650(0.9); 1.350(2.8); 1.330(2.6); 1.314(1.8); 1.297(2.0);1.265(2.7); 1.236(4.8); 1.197(3.2); 1.164(1.5); 1.143(0.5); 0.798(13.9);0.791(16.0); 0.783(15.7); 0.775(13.1); 0.146(0.6); 0.008(5.0);0.000(123.5); −0.008(4.8); −0.150(0.6) Example I-32: ¹H-NMR(400.0 MHz,CD3CN): δ = 12.090(0.9); 8.462(5.1); 8.287(3.2); 8.275(3.3); 8.249(0.4);8.178(1.1); 8.110(2.2); 8.095(6.5); 7.734(4.6); 7.472(2.8); 7.460(2.7);5.365(0.4); 4.512(2.8); 4.475(3.4); 4.153(3.5); 4.117(2.9); 4.013(2.0);3.412(0.6); 3.408(0.8); 3.394(1.4); 3.390(2.3); 3.376(2.6); 3.373(2.7);3.359(2.3); 3.355(1.5); 3.342(0.8); 3.338(0.7); 3.157(7.3); 2.892(1.5);2.776(1.3); 2.191(16.5); 2.115(0.3); 2.108(0.4); 1.996(0.4); 1.965(1.5);1.959(3.7); 1.953(19.8); 1.947(35.8); 1.941(47.9); 1.935(32.6);1.929(16.8); 1.769(0.3); 1.430(0.8); 1.372(0.4); 1.348(1.6); 1.341(0.8);1.285(0.8); 1.277(0.6); 1.269(0.8); 1.263(0.5); 1.223(0.5); 1.206(0.4);1.189(15.7); 1.152(16.0); 1.122(0.3); 1.011(5.6); 0.994(11.3);0.976(5.5); 0.146(0.7); 0.008(6.0); 0.000(156.9); −0.009(6.7);−0.150(0.7) Example I-33: ¹H-NMR(400.1 MHz, CDCl3): δ = 8.246(1.6);7.614(1.6); 7.562(1.0); 7.541(1.1); 7.276(0.6); 7.056(0.9); 7.034(0.8);6.467(1.7); 4.490(0.5); 4.455(1.2); 4.405(1.0); 4.370(0.5); 3.100(1.2);3.088(1.4); 2.042(0.7);1.258(0.5); 1.045(16.0)1H-NMR Data for Compounds in Table 2 Written in Classical Form

Ex-no NMR V-3 1H-NMR (400 MHz, d3-CD3CN): δ = 8.14 (d, 1H), 7.55-7.53(dd, 1H), 7.34 (d, 1H), 3.89 (s, 2H), 1.19 (s, 9H) ppm V-4 1H-NMR (400MHz, d3-CD3CN): δ = 8.28-8.27 (dd, 1H), 7.61-7.59 (dd, 1H), 7.31-7.28(dd, 1H), 4.04 (s, 2H), 1.24 (s, 9H) ppm V-5 1H-NMR (400 MHz, d3-CD3CN):δ = 8.54 (s, 1H), 8.40 (d, 1H), 7.18 (d, 1H), 4.02 (s, 2H), 1.80-1.71(m, 2H), 1.62-1.53 (m, 2H), 1.15 (s, 3H), 0.83 (t, 6H) ppm V-6 1H-NMR(400 MHz, d3-CD3CN): δ = 8.53 (s, 1H), 8.40 (d, 1H), 7.20 (d, 1H), 4.05(s, 2H), 1.97(m, 1H), 1.12 (s, 6H), 0.87 (d, 3H) ppmNMR-Peak Lists for Compounds in Table 2

Example V-1: 1H-NMR(300.2 MHz, CDCl3): δ = 8.416(0.7); 8.409(0.7);7.704(0.7); 7.696(0.7); 7.262(6.2); 4.197(2.8); 1.568(2.6); 1.264(16.0);1.252(0.6); 1.245(3.0); 0.000(3.0) Example V-2: 1H-NMR(400.1 MHz,CDCl3): δ = 8.727(0.6); 8.722(0.7); 8.095(0.4); 8.074(0.4); 7.986(0.5);7.982(0.6); 7.789(0.4); 7.768(0.4); 7.679(0.5); 7.527(0.5); 7.262(0.9);3.988(2.4); 1.715(0.7); 1.264(16.0); 0.000(0.7) Example V-7:1H-NMR(400.0 MHz, DMSO): δ = 8.429(0.5); 8.425(0.6); 8.417(0.6);8.413(0.5); 8.357(0.8); 8.352(0.8); 7.561(0.5); 7.546(0.3); 7.542(0.5);7.334(0.5); 7.322(0.5); 7.315(0.4); 7.303(0.4); 3.965(3.3); 3.330(1.9);2.507(2.4); 2.503(3.1); 2.499(2.4); 1.275(0.5); 1.170(16.0); 0.000(2.9)Example V-8: 1H-NMR(400.0 MHz, DMSO): δ = 8.475(1.2); 8.471(0.8);8.464(0.8); 8.460(1.2); 7.182(1.1); 7.179(0.8); 7.171(0.8); 7.168(1.1);3.973(2.8); 3.323(1.3); 2.510(2.4); 2.506(4.4); 2.502(5.5); 2.497(4.0);2.493(1.9); 1.158(16.0);0.000(0.7)1H-NMR Data for Compounds in Table 3 Written in Classical Form

Ex-no NMR XII-3 1H-NMR (400 MHz, d3-CD3CN): δ = 8.14 (d, 1H), 7.56-7.53(dd, 1H), 7.28 (d, 1H), 3.08 (s, 2H), 2.62 (d, 1H), 1.87 (d, 1H), 1.00(s, 9H) ppm XII-4 1H-NMR (400 MHz, d3-CD3CN): δ = 8.24-8.23 (dd, 1H),7.59-7.57 (dd, 1H), 7.25-7.22 (dd, 1H), 3.31 (d, 1H), 3.16 (d, 1H), 2.63(m, 1H), 1.76 (m, 1H), 1.04 (s, 9H) ppm XII-5 1H-NMR (400 MHz,d3-CD3CN): δ = 8.49 (s, 1H), 8.33 (d, 1H), 7.18 (d, 1H), 3.34 (d, 1H),3.19 (d, 1H), 2.63 (d, 1H), 1.83 (d, 1H), 1.04 (s, 9H) ppmNMR-Peak Lists for Compounds in Table 3

Example XII-1: ¹H-NMR(300.2 MHz, CDCl3): δ = 8.372(0.8); 8.365(0.8);7.659(0.9); 7.652(0.9); 7.263(1.7); 4.196(0.3); 3.555(0.3); 3.553(0.3);3.510(0.6); 3.507(0.6); 3.380(0.9); 3.334(0.5); 2.698(0.5); 2.695(0.5);2.684(0.5); 2.682(0.5); 2.138(0.8); 2.124(0.8); 1.264(1.9); 1.245(1.5);1.166(0.6); 1.152(0.3); 1.061(16.0); 1.034(0.3); 0.000(1.7) ExampleXII-2: ¹H-NMR(400.1 MHz, CDCl3): δ = 8.720(0.8); 8.714(0.8); 8.085(0.5);8.064(0.5); 7.941(0.6); 7.936(0.6); 7.777(0.4); 7.757(0.5); 7.672(0.3);7.669(0.5); 7.539(0.3); 7.537(0.3); 7.519(0.5); 7.262(1.1); 3.259(0.8);3.238(1.1); 2.635(0.6);2.625(0.6); 1.952(0.9); 1.942(0.9); 1.717(0.4);1.159(0.6); 1.084(16.0); 0.000(0.8) Example XII-16: ¹H-NMR(400.0 MHz,CD3CN): δ = 4.494(9.6); 2.031(0.5); 2.013(1.2); 1.996(1.6); 1.979(1.3);1.962(0.6); 1.953(0.6); 1.946(1.1); 1.940(1.4); 1.934(1.0); 1.928(0.5);1.160(0.6); 1.057(16.0); 0.819(11.7); 0.802(11.9); 0.000(0.6)

Use Examples Example A In Vivo Preventive Test on Botrytis cinerea (GreyMould)

The tested active ingredients are prepared by homogenization in amixture of acetone/Dimethyl sulfoxide/Tween®, and then diluted withwater to obtain the desired active material concentration.

The young plants of gherkin are treated by spraying the activeingredient prepared as described above. Control plants are treated onlywith an aqueous solution of acetone/Dimethyl sulfoxide/Tween®.

After 24 hours, the plants are contaminated by spraying the leaves withan aqueous suspension of Botrytis cinerea spores. The contaminatedgherkin plants are incubated for 4 to 5 days at 17° C. and at 90%relative humidity.

The test is evaluated 4 to 5 days after the inoculation. 0% means anefficacy which corresponds to that of the control plants while anefficacy of 100% means that no disease is observed.

In this test the following compounds according to the invention showedefficacy of at least 70% at a concentration of 500 ppm of activeingredient.

Ex_no. Eff. % I-3 100 I-27 100 I-29 100

In this test the following compounds according to the invention showedefficacy of at least 70% at a concentration of 100 ppm of activeingredient.

Ex_no. Eff. % I-5 89 I-6 100 I-7 97 I-14 87

Example B In Vivo Preventive Test on Puccinia recondita (Brown Rust onWheat)

The tested active ingredients are prepared by homogenization in amixture of acetone/Dimethyl sulfoxide/Tween®, and then diluted withwater to obtain the desired active material concentration.

The young plants of wheat are treated by spraying the active ingredientprepared as described above. Control plants are treated only with anaqueous solution of acetone/Dimethyl sulfoxide/Tween®.

After 24 hours, the plants are contaminated by spraying the leaves withan aqueous suspension of Puccinia recondita spores. The contaminatedwheat plants are incubated for 24 hours at 20° C. and at 100% relativehumidity and then for 10 days at 20° C. and at 70-80% relative humidity.

The test is evaluated 11 days after the inoculation. 0% means anefficacy which corresponds to that of the control plants while anefficacy of 100% means that no disease is observed.

In this test the following compounds according to the invention showedefficacy of at least 70% at a concentration of 500 ppm of activeingredient.

Ex_no. Eff. % I-3 97 I-24 86 I-25 71 I-26 89 I-27 98 I-29 100 I-30 94I-31 89 I-32 83

In this test the following compounds according to the invention showedefficacy of at least 70% at a concentration of 100 ppm of activeingredient.

Ex_no. Eff. % I-4 88 I-5 90 I-6 88 I-7 81

Example C In Vivo Preventive Test on Pyrenophora teres (Net Blotch onBarley)

The tested active ingredients are prepared by homogenization in amixture of acetone/Dimethyl sulfoxide/Tween®, and then diluted withwater to obtain the desired active material concentration.

The young plants of barley are treated by spraying the active ingredientprepared as described above. Control plants are treated only with anaqueous solution of acetone/Dimethyl sulfoxide/Tween®.

After 24 hours, the plants are contaminated by spraying the leaves withan aqueous suspension of Pyrenophora teres spores. The contaminatedbarley plants are incubated for 48 hours at 20° C. and at 100% relativehumidity and then for 12 days at 20° C. and at 70-80% relative humidity.

The test is evaluated 14 days after the inoculation. 0% means anefficacy which corresponds to that of the control plants while anefficacy of 100% means that no disease is observed.

In this test the following compounds according to the invention showedefficacy of at least 70% at a concentration of 500 ppm of activeingredient.

Ex_no. Eff. % I-24 75 I-26 71 I-27 97 I-29 93 I-30 71

In this test the following compounds according to the invention showedefficacy of at least 70% at a concentration of 100 ppm of activeingredient.

Ex_no. Eff. % I-4 83 I-5 83

Example D In Vivo Preventive Test on Pyricularia oryzae (Rice Blast)

The tested active ingredients are prepared by homogenization in amixture of acetone/Dimethyl sulfoxide/Tween®, and then diluted withwater to obtain the desired active material concentration.

The young plants of rice are treated by spraying the active ingredientprepared as described above. Control plants are treated only with anaqueous solution of acetone/Dimethyl sulfoxide/Tween®.

After 24 hours, the plants are contaminated by spraying the leaves withan aqueous suspension of Pyricularia oryzae spores. The contaminatedrice plants are incubated at 25° C. and at 80% relative humidity.

The test is evaluated 6 days after the inoculation. 0% means an efficacywhich corresponds to that of the control plants while an efficacy of100% means that no disease is observed.

In this test the following compounds according to the invention showedefficacy of at least 70% at a concentration of 500 ppm of activeingredient.

Ex_no. Eff. % I-3 88

Example E In Vivo Preventive Test on Septoria tritici (Leaf Spot onWheat)

The tested active ingredients are prepared by homogenization in amixture of acetone/Dimethyl sulfoxide/Tween®, and then diluted withwater to obtain the desired active material concentration.

The young plants of wheat are treated by spraying the active ingredientprepared as described above. Control plants are treated only with anaqueous solution of acetone/Dimethyl sulfoxide/Tween®.

After 24 hours, the plants are contaminated by spraying the leaves withan aqueous suspension of Septoria tritici spores. The contaminated wheatplants are incubated for 72 hours at 18° C. and at 100% relativehumidity and then for 21 days at 20° C. and at 90% relative humidity.

The test is evaluated 24 days after the inoculation. 0% means anefficacy which corresponds to that of the control plants while anefficacy of 100% means that no disease is observed.

In this test the following compounds according to the invention showedefficacy of at least 70% at a concentration of 500 ppm of activeingredient.

Ex_no. Eff. % I-3 100 I-24 100 I-26 97 I-27 97 I-29 100 I-30 100 I-31100

In this test the following compounds according to the invention showedefficacy of at least 70% at a concentration of 100 ppm of activeingredient.

Ex_no. Eff. % I-5 97 I-6 98 I-7 81

Example F In Vivo Preventive Test on Sphaerotheca fuliginea (PowderyMildew on Cucurbits)

The tested active ingredients are prepared by homogenization in amixture of acetone/Dimethyl sulfoxide/Tween®, and then diluted withwater to obtain the desired active material concentration.

The young plants of gherkin are treated by spraying the activeingredient prepared as described above. Control plants are treated onlywith an aqueous solution of acetone/Dimethyl sulfoxide/Tween®.

After 24 hours, the plants are contaminated by spraying the leaves withan aqueous suspension of Sphaerotheca fuliginea spores. The contaminatedgherkin plants are incubated for 72 hours at 18° C. and at 100% relativehumidity and then for 12 days at 20° C. and at 70-80% relative humidity.

The test is evaluated 15 days after the inoculation. 0% means anefficacy which corresponds to that of the control plants while anefficacy of 100% means that no disease is observed.

In this test the following compounds according to the invention showedefficacy of at least 70% at a concentration of 500 ppm of activeingredient.

Ex_no. Eff. % I-2 98 I-3 100 I-24 100 I-26 100 I-27 100 I-29 100 I-30100 I-31 100 I-32 98

In this test the following compounds according to the invention showedefficacy of at least 70% at a concentration of 100 ppm of activeingredient.

Ex_no. Eff. % I-4 100 I-5 100 I-6 100 I-7 100 I-8 79 I-9 97 I-10 97 I-14100 I-15 100 I-16 100

Example G In Vivo Preventive Test on Uromyces appendiculatus (Bean Rust)

The tested active ingredients are prepared by homogenization in amixture of acetone/Dimethyl sulfoxide/Tween®, and then diluted withwater to obtain the desired active material concentration.

The young plants of bean are treated by spraying the active ingredientprepared as described above. Control plants are treated only with anaqueous solution of acetone/Dimethyl sulfoxide/Tween®.

After 24 hours, the plants are contaminated by spraying the leaves withan aqueous suspension of Uromyces appendiculatus spores. Thecontaminated bean plants are incubated for 24 hours at 20° C. and at100% relative humidity and then for 10 days at 20° C. and at 70-80%relative humidity.

The test is evaluated 11 days after the inoculation. 0% means anefficacy which corresponds to that of the control plants while anefficacy of 100% means that no disease is observed.

In this test the following compounds according to the invention showedefficacy of at least 70% at a concentration of 500 ppm of activeingredient.

Ex_no. Eff. % I-2 77 I-3 100 I-24 97 I-26 100 I-27 100 I-29 100 I-30 100I-31 96 I-32 99

In this test the following compounds according to the invention showedefficacy of at least 70% at a concentration of 100 ppm of activeingredient.

Ex_no. Eff. % I-4 100 I-5 100 I-6 100 I-7 100 I-10 85 I-15 91 I-16 84

Example H Blumeria Test (Barley)/Preventive

Solvent: 49 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound or active compound combination is mixed with thestated amounts of solvent and emulsifier, and the concentrate is dilutedwith water to the desired concentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound or active compound combination at thestated rate of application.

After the spray coating has been dried, the plants are dusted withspores of Blumeria graminis fsp. hordei.

The plants are placed in the greenhouse at a temperature ofapproximately 18° C. and a relative atmospheric humidity ofapproximately 80% to promote the development of mildew pustules.

The test is evaluated 7 days after the inoculation. 0% means an efficacywhich corresponds to that of the untreated control, while an efficacy of100% means that no disease is observed.

In this test the following compounds according to the invention showedan efficacy of 70% or even higher at a concentration of 500 ppm ofactive ingredient.

Ex_no. Eff. % I-3 100 I-4 100 I-5 100 I-6 100 I-7 100 I-27 100 I-29 100I-30 100

Example I Fusarium culmorum-Test (Wheat)/Preventive

Solvent: 49 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound or active compound combination is mixed with thestated amounts of solvent and emulsifier, and the concentrate is dilutedwith water to the desired concentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound or active compound combination at thestated rate of application. After the spray coating has been dried, theplants are slightly injured by using a sandblast and afterwards they aresprayed with a conidia suspension of Fusarium culmorum.

The plants are placed in the greenhouse under a translucent incubationcabinet at a temperature of approximately 22° C. and a relativeatmospheric humidity of approximately 100%.

The test is evaluated 5 days after the inoculation. 0% means an efficacywhich corresponds to that of the untreated control, while an efficacy of100% means that no disease is observed.

In this test the following compounds according to the invention showedan efficacy of 70% or even higher at a concentration of 500 ppm ofactive ingredient.

Ex_no. Eff. % I-3 100 I-4 93 I-5 100 I-6 100 I-7 100 I-27 100 I-29 100

Example J Fusarium graminearum-Test (Barley)/Preventive

Solvent: 49 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound or active compound combination is mixed with thestated amounts of solvent and emulsifier, and the concentrate is dilutedwith water to the desired concentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound or active compound combination at thestated rate of application.

After the spray coating has been dried, the plants are slightly injuredby using a sandblast and afterwards they are sprayed with a conidiasuspension of Fusarium graminearum.

The plants are placed in the greenhouse under a translucent incubationcabinet at a temperature of approximately 22° C. and a relativeatmospheric humidity of approximately 100%.

The test is evaluated 5 days after the inoculation. 0% means an efficacywhich corresponds to that of the untreated control, while an efficacy of100% means that no disease is observed.

In this test the following compounds according to the invention showedan efficacy of 70% or even higher at a concentration of 500 ppm ofactive ingredient.

Ex_no. Eff. % I-3 100 I-4 92 I-5 100 I-6 100 I-7 100 I-27 100 I-29 100

Example K Fusarium nivale (Var. Majus)-Test (Wheat)/Preventive

Solvent: 49 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound or active compound combination is mixed with thestated amounts of solvent and emulsifier, and the concentrate is dilutedwith water to the desired concentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound or active compound combination at thestated rate of application.

After the spray coating has been dried, the plants are slightly injuredby using a sandblast and afterwards they are sprayed with a conidiasuspension of Fusarium nivale (var. majus).

The plants are placed in the greenhouse under a translucent incubationcabinet at a temperature of approximately 10° C. and a relativeatmospheric humidity of approximately 100%.

The test is evaluated 5 days after the inoculation. 0% means an efficacywhich corresponds to that of the untreated control, while an efficacy of100% means that no disease is observed.

In this test the following compounds according to the invention showedan efficacy of 70% or even higher at a concentration of 500 ppm ofactive ingredient.

Ex_no. Eff. % I-3 100 I-4 100 I-5 100 I-6 100 I-7 100 I-27 100 I-29 100I-30 100

Example L Leptosphaeria nodorum Test (Wheat)/Preventive

Solvent: 49 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound or active compound combination is mixed with thestated amounts of solvent and emulsifier, and the concentrate is dilutedwith water to the desired concentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound or active compound combination at thestated rate of application.

After the spray coating has been dried, the plants are sprayed with aspore suspension of Leptosphaeria nodorum. The plants remain for 48hours in an incubation cabinet at approximately 20° C. and a relativeatmospheric humidity of approximately 100%.

The plants are placed in the greenhouse at a temperature ofapproximately 22° C. and a relative atmospheric humidity ofapproximately 80%.

The test is evaluated 8 days after the inoculation. 0% means an efficacywhich corresponds to that of the untreated control, while an efficacy of100% means that no disease is observed.

In this test the following compounds according to the invention showedan efficacy of 70% or even higher at a concentration of 500 ppm ofactive ingredient.

Ex_no. Eff. % I-3 100 I-4 88 I-5 100 I-6 100 I-7 100 I-27 88 I-29 100I-30 88

Example M Phakopsora Test (Soybeans)/Preventive

Solvent: 24.5 parts by weight of acetone

-   -   24.5 parts by weight of dimethylacetamide        Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound at the stated rate of application. Afterthe spray coating has dried on, the plants are inoculated with anaqueous spore suspension of the causal agent of soybean rust (Phakopsorapachyrhizi) and stay for 24 h without light in an incubation cabinet atapproximately 24° C. and a relative atmospheric humidity of 95%.

The plants remain in the incubation cabinet at approximately 24° C. anda relative atmospheric humidity of approximately 80% and a day/nightinterval of 12 h.

The test is evaluated 7 days after the inoculation. 0% means an efficacywhich corresponds to that of the untreated control, while an efficacy of100% means that no disease is observed.

In this test the following compounds according to the invention showedefficacy of 70% or even higher at a concentration of 100 ppm of activeingredient.

Ex_no. Eff. % I-3 100 I-4 99 I-6 99

In this test the following compounds according to the invention showedefficacy of 70% or even higher at a concentration of 10 ppm of activeingredient.

Ex_no. Eff. % I-27 75 I-29 78

Example N Podosphaera Test (Apples)/Preventive

Solvent: 24.5 parts by weight of acetone

-   -   24.5 parts by weight of dimethylacetamide        Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound at the stated rate of application. Afterthe spray coating has dried on, the plants are inoculated with anaqueous spore suspension of the causal agent of apple mildew(Podosphaera leucotricha). The plants are then placed in a greenhouse atapproximately 23° C. and a relative atmospheric humidity ofapproximately 70%.

The test is evaluated 10 days after the inoculation. 0% means anefficacy which corresponds to that of the untreated control, while anefficacy of 100% means that no disease is observed.

In this test the following compounds according to the invention showedefficacy of 70% or even higher at a concentration of 100 ppm of activeingredient.

Ex_no. Eff. % I-3 100

Example O Pyricularia oryzae-Test (Rice)/Preventive

Solvent: 49 parts by weight of N,N-dimethylacetamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound or active compound combination is mixed with thestated amounts of solvent and emulsifier, and the concentrate is dilutedwith water to the desired concentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound or active compound combination at thestated rate of application.

After the spray coating has been dried, the plants are sprayed with aspore suspension of Pyricularia oryzae. The plants remain for 25 hoursin an incubation cabinet at approximately 25° C. and a relativeatmospheric humidity of approximately 100%.

The plants are placed in the greenhouse under a translucent incubationscabinet at a temperature of approximately 25° C. and a relativeatmospheric humidity of approximately 100%.

The test is evaluated 8 days after the inoculation. 0% means an efficacywhich corresponds to that of the control, while an efficacy of 100%means that no disease is observed.

In this test the following compounds according to the invention showedan efficacy of 70% or even higher at a concentration of 500 ppm ofactive ingredient.

Ex_no. Eff. % I-3 75 I-5 93 I-6 94 I-7 89 I-29 71

Example P Venturia Test (Apples)/Preventive

Solvent: 24.5 parts by weight of acetone

-   -   24.5 parts by weight of dimethylacetamide        Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound at the stated rate of application. Afterthe spray coating has dried on, the plants are inoculated with anaqueous conidia suspension of the causal agent of apple scab (Venturiainaequalis) and then remain for 1 day in an incubation cabinet atapproximately 20° C. and a relative atmospheric humidity of 100%.

The plants are then placed in a greenhouse at approximately 21° C. and arelative atmospheric humidity of approximately 90%.

The test is evaluated 10 days after the inoculation. 0% means anefficacy which corresponds to that of the untreated control, while anefficacy of 100% means that no disease is observed.

In this test the following compounds according to the invention showedefficacy of 70% or even higher at a concentration of 100 ppm of activeingredient.

Ex_no. Eff. % I-3 100 I-4 94 I-6 96

The invention claimed is:
 1. Triazole derivative of formula (I)

wherein R¹ represents substituted or non-substituted C₁-C₈-alkyl;substituted or non-substituted C₄-C₈-cycloalkylalkyl; substituted ornon-substituted C₂-C₈-alkenyl; substituted or non-substitutedC₂-C₈-alkynyl; R² represents H, C₁-C₈-alkyl,—Si(R^(3a))(R^(3b))(R^(3c)), —P(O)(OH)₂, —CH₂—O—P(O)(OH)₂, substitutedor non-substituted —C(O)—C₁-C₈-alkyl; substituted or non-substituted—C(O)—C₃-C₇-cycloalkyl, substituted or non-substituted—C(O)NH—C₁-C₈-alkyl; substituted or non-substituted—C(O)N-di-C₁-C₈-alkyl; substituted or non-substituted—C(O)O—C₁-C₈-alkyl; R^(3a), R^(3b), R^(3c) independent from each otherrepresent a substituted or non-substituted C₁-C₈-alkyl; and X representsa substituted or non-substituted unsaturated 6-membered heterocyclecontaining 1 or 2 nitrogen atom(s) as heteroatom(s) or a benzannulatedderivative thereof; and/or salt and/or N-oxide thereof.
 2. Triazolederivative of formula (I) and/or salt and/or N-oxide according to claim1, wherein R¹ represents substituted or non-substituted C₁-C₈-alkyl;substituted or non-substituted C₄-C₈-cycloalkylalkyl; substituted ornon-substituted C₂-C₈-alkenyl; substituted or non-substitutedC₂-C₈-alkynyl; R² represents H, C₁-C₈-alkyl,—Si(R^(3a))(R^(3b))(R^(3c)), —P(O)(OH)₂, —CH₂—O—P(O)(OH)₂, substitutedor non-substituted —C(O)—C₁-C₈-alkyl; substituted or non-substituted—C(O)—C₃-C₇-cycloalkyl, substituted or non-substituted—C(O)NH—C₁-C₈-alkyl; substituted or non-substituted—C(O)N-di-C₁-C₈-alkyl; substituted or non-substituted—C(O)O—C₁-C₈-alkyl; R^(3a), R^(3b), R^(3c) independent from each otherrepresent a substituted or non-substituted C₁-C₈-alkyl; and X representsa substituted or non-substituted unsaturated 6 membered heterocyclecontaining 1 or 2 nitrogen atom(s) as heteroatom(s) or a benzannulatedderivative thereof, with the proviso that X does not represent2-pyridinyl.
 3. Triazole derivative of formula (I) and/or salt and/orN-oxide according to claim 1, wherein R¹ represents substituted ornon-substituted C₁-C₈-alkyl; R² represents H, C₁-C₈-alkyl, substitutedor non-substituted —C(O)—C₁-C₈-alkyl; and X represents a substituted ornon-substituted 3-pyridinyl, 4-pyridinyl, 4-pyrimidinyl, 5-pyrimidinyl,pyrazin-2-yl, pyridazin-3-yl, pyridazin-4-yl, quinoline-2-yl orquinoline-3-yl.
 4. Method for controlling one or more harmfulmicroorganisms, comprising applying a compound of formula (I) and/orsalt and/or N-oxide according to claim 1 to the harmful microorganismsand/or a habitat thereof.
 5. Method for controlling phytopathogenicharmful fungi, comprising applying a compound of formula (I) and/or saltand/or N-oxide according to claim 1 to the phytopathogenic harmful fungiand/or a habitat thereof.
 6. Composition for controlling harmfulmicroorganisms, comprising a content of at least one compound of formula(I) and/or salt and/or N-oxide according to claim 1, in addition to oneor more extenders and/or surfactants.
 7. Composition according to claim6 comprising at least one further active ingredient selected from thegroup of the insecticides, attractants, sterilants, bactericides,acaricides, nematicides, fungicides, growth regulators, herbicides,fertilizers, safeners and semiochemicals.
 8. The composition accordingto claim 6 for control of phytopathogenic harmful fungi.
 9. Process forproducing a composition for controlling one or more harmfulmicroorganisms, comprising mixing a compound of formula (I) according toclaim 1 with one or more extenders and/or surfactants.
 10. The method ofclaim 4 comprising treatment of one or more transgenic plants.
 11. Seedtreated with the compound of formula (I) and/or salt and/or N-oxideaccording to claim
 1. 12. Compound of formula (V)

wherein X represents a substituted or non-substituted 3-pyridinyl or4-pyridinyl or a benzannulated derivative thereof; and R¹ represents2-methyl-butan-2-yl, 3-methyl-pentan-3-yl or 2,3-dimethyl-butan-2-yl;and/or a salt and/or N-oxide thereof.
 13. Epoxide of formula (XII)

wherein X represents a substituted or non-substituted unsaturated6-membered heterocycle containing 1 or 2 nitrogen atom(s) asheteroatom(s) or a benzannulated derivative thereof; and R¹ representssubstituted or non-substituted C₂-C₈-alkyl; substituted ornon-substituted C₄-C₈-cycloalkylalkyl; substituted or non-substitutedC₂-C₈-alkenyl; substituted or non-substituted C₂-C₈-alkynyl; and/or asalt and/or N-oxide thereof.
 14. Alcohol of formula (XV)

wherein X represents a substituted or non-substituted unsaturated6-membered heterocycle containing 1 or 2 nitrogen atom(s) asheteroatom(s) or a benzannulated derivative thereof; R¹ representssubstituted or non-substituted C₁-C₈-alkyl; substituted ornon-substituted C₄-C₈-cycloalkylalkyl; substituted or non-substitutedC₂-C₈-alkenyl; substituted or non-substituted C₂-C₈-alkynyl; and Arepresents chlorine, bromine, iodine, O—SO₂— C₁-C₈-alkyl or O—SO₂-aryl;and/or a salt and/or N-oxide thereof.